Vessel inspection apparatus and methods

ABSTRACT

Methods for processing a vessel, for example to provide a gas barrier or lubricity, are disclosed. First and second PECVD or other vessel processing stations or devices and a vessel holder comprising a vessel port are provided. An opening of the vessel can be seated on the vessel port. The interior surface of the seated vessel can be processed via the vessel port by the first and second processing stations or devices. Vessel barrier, lubricity and hydrophobic coatings and coated vessels, for example syringes and medical sample collection tubes are disclosed. A vessel processing system and vessel inspection apparatus and methods are also disclosed.

This is a continuation of U.S. Ser. No. 13/169,811, filed Jun. 27, 2011,now U.S. Pat. No. 8,512,796, which is a divisional of U.S. Ser. No.12/779,007, filed May 12, 2010, now U.S. Pat. No. 7,985,188, whichclaims the priority of U.S. Provisional Ser. Nos. 61/177,984 filed May13, 2009; 61/222,727, filed Jul. 2, 2009; 61/213,904, filed Jul. 24,2009; 61/234,505, filed Aug. 17, 2009; 61/261,321, filed Nov. 14, 2009;61/263,289, filed Nov. 20, 2009; 61/285,813, filed Dec. 11, 2009;61/298,159, filed Jan. 25, 2010; 61/299,888, filed Jan. 29, 2010;61/318,197, filed Mar. 26, 2010, and 61/333,625, filed May 11, 2010.These applications are incorporated here by reference in their entirety.

Also incorporated by reference in their entirety are the followingEuropean patent applications, all filed May 12, 2010: EP10162755.2;EP10162760.2; EP10162756.0; EP10162758.6; EP10162761.0; andEP10162757.8.

The present invention also relates to the technical field of fabricationof coated vessels for storing biologically active compounds or blood.For example, the invention relates to a vessel processing system forcoating of a vessel, vessel processing system for coating and inspectionof a vessel, to a portable vessel holder for a vessel processing system,to a plasma enhanced chemical vapor deposition apparatus for coating aninterior surface of a vessel, to a method for coating an interiorsurface of a vessel, to a method for coating and inspection of a vessel,to a method of processing a vessel, to the use of a vessel processingsystem, to a computer-readable medium and to a program element.

The present disclosure also relates to improved methods for processingvessels, for example multiple identical vessels used for venipunctureand other medical sample collection, pharmaceutical preparation storageand delivery, and other purposes. Such vessels are used in large numbersfor these purposes, and must be relatively economical to manufacture andyet highly reliable in storage and use.

BACKGROUND OF THE INVENTION

Evacuated blood collection tubes are used for drawing blood from apatient for medical analysis. The tubes are sold evacuated. Thepatient's blood is communicated to the interior of a tube by insertingone end of a double-ended hypodermic needle into the patient's bloodvessel and impaling the closure of the evacuated blood collection tubeon the other end of the double-ended needle. The vacuum in the evacuatedblood collection tube draws the blood (or more precisely, the bloodpressure of the patient pushes the blood) through the needle into theevacuated blood collection tube, increasing the pressure within the tubeand thus decreasing the pressure difference causing the blood to flow.The blood flow typically continues until the tube is removed from theneedle or the pressure difference is too small to support flow.

Evacuated blood collection tubes should have a substantial shelf life tofacilitate efficient and convenient distribution and storage of thetubes prior to use. For example, a one-year shelf life is desirable, andprogressively longer shelf lives, such as 18 months, 24 months, or 36months, are also desired in some instances. The tube desirably remainsessentially fully evacuated, at least to the degree necessary to drawenough blood for analysis (a common standard is that the tube retains atleast 90% of the original draw volume), for the full shelf life, withvery few (optimally no) defective tubes being provided.

A defective tube is likely to cause the phlebotomist using the tube tofail to draw sufficient blood. The phlebotomist might then need toobtain and use one or more additional tubes to obtain an adequate bloodsample.

Prefilled syringes are commonly prepared and sold so the syringe doesnot need to be filled before use. The syringe can be prefilled withsaline solution, a dye for injection, or a pharmaceutically activepreparation, for some examples.

Commonly, the prefilled syringe is capped at the distal end, as with acap, and is closed at the proximal end by its drawn plunger. Theprefilled syringe can be wrapped in a sterile package before use. To usethe prefilled syringe, the packaging and cap are removed, optionally ahypodermic needle or another delivery conduit is attached to the distalend of the barrel, the delivery conduit or syringe is moved to a useposition (such as by inserting the hypodermic needle into a patient'sblood vessel or into apparatus to be rinsed with the contents of thesyringe), and the plunger is advanced in the barrel to inject thecontents of the barrel.

One important consideration in manufacturing pre-filled syringes is thatthe contents of the syringe desirably will have a substantial shelflife, during which it is important to isolate the material filling thesyringe from the barrel wall containing it, to avoid leaching materialfrom the barrel into the prefilled contents or vice versa.

Since many of these vessels are inexpensive and used in largequantities, for certain applications it will be useful to reliablyobtain the necessary shelf life without increasing the manufacturingcost to a prohibitive level. It is also desirable for certainapplications to move away from glass vessels, which can break and areexpensive to manufacture, in favor of plastic vessels which are rarelybroken in normal use (and if broken do not form sharp shards fromremnants of the vessel, like a glass tube would). Glass vessels havebeen favored because glass is more gas tight and inert to pre-filledcontents than untreated plastics. Also, due to its traditional use,glass is well accepted, as it is known to be relatively innocuous whencontacted with medical samples or pharmaceutical preparations and thelike.

A further consideration when regarding syringes is to ensure that theplunger can move at a constant speed and with a constant force when itis pressed into the barrel. For this purpose, a lubricity layer, eitheron one or on both of the barrel and the plunger, is desirable.

SUMMARY OF THE INVENTION

VI. Vessel Inspection

VI.A. Vessel Processing Including Pre-Coating and Post-CoatingInspection

An aspect of the invention is a vessel processing method for processinga plastic vessel having an opening and a wall defining an interiorsurface. The method can be carried out, for example, by inspecting theinterior surface of the vessel as provided for defects; applying acoating to the interior surface of the vessel after inspecting thevessel as provided; and inspecting the coating for defects.

Another aspect of the invention is a vessel processing method in which abarrier layer is applied to the vessel after inspecting the vessel asmolded, and the interior surface of the vessel is inspected for defectsafter applying the barrier layer.

VI.B. Vessel Inspection by Detecting Outgassing of Container Wall, e.g.Through Barrier Layer

Another aspect of the invention is a method for inspecting a coating bymeasuring a volatile species outgassed by the coated article(“outgassing method”). The method can be used for inspecting the productof a coating process wherein a coating has been applied to the surfaceof a substrate to form a coated surface. For example, the method can beused as an inline process control for a coating process, to identify andeliminate coated products not meeting a predetermined standard ordamaged coating products.

Generally, the “volatile species” is a gas or vapor at test conditions,optionally is selected from the group consisting of air, nitrogen,oxygen, water vapor, volatile coating components, volatile substratecomponents, and a combination thereof, optionally is air, nitrogen,oxygen, water vapor, or a combination thereof. The method can be used tomeasure just one or a few volatile species, but optionally a pluralityof different volatile species is measured in step (c) below, andoptionally substantially all the volatile species released from theinspection object are measured in step (c) below.

The outgassing method comprises:

(a) providing the product as inspection object;

(c) measuring the release of at least one volatile species from theinspection object into the gas space adjacent to the coated surface; and

(d) comparing the result of step (c) with the result of step (c) for atleast one reference object measured under the same test conditions, thusdetermining the presence or absence of the coating, and/or a physicaland/or chemical property of the coating.

In the outgassing method, the physical and/or chemical property of thecoating to be determined can be selected from the group consisting ofits barrier effect, its wetting tension, and its composition, andoptionally is its barrier effect.

Advantageously, step (c) is performed by measuring the mass flow rate orvolume flow rate of the at least one volatile species in the gas spaceadjacent to the coated surface.

Optionally, the reference object (i) is an uncoated substrate; or (ii)is a substrate coated with a reference coating. This depends on, e.g.,whether the outgassing method is used to determine the presence orabsence of a coating (then the reference object can be an uncoatedsubstrate) or to determine the properties of the coating, e.g. incomparison to a coating with known properties. For determining thecoating's identity with a specific coating, a reference coating willalso be a typical choice.

The outgassing method can also comprise as an additional step betweensteps (a) and (c) the step of (b) changing the pressure in the gas spaceadjacent to the coated surface such that a higher mass flow rate orvolume flow rate of the volatile species can be realized than withoutthe pressure differential. The pressure differential can e.g. beprovided by at least partially evacuating the gas space in the vessel.In this case, the volatile species can be measured which is outgassedinto the lumen of the vessel.

If a vacuum is applied to create a pressure differential, themeasurement can be performed by using a measurement cell interposedbetween the coated surface of the substrate and a source of vacuum.

In one aspect, the inspection object can be contacted with a volatilespecies in step (a), optionally a volatile species selected from thegroup consisting of air, nitrogen, oxygen, water vapor, and acombination thereof, optionally in order to allow the adsorption orabsorption of the volatile species onto or into the material of theinspection object. Then, the subsequent release of the volatile speciesfrom the inspection object is measured in step (c). As differentmaterials (like, e.g., the coating and the substrate) have differentadsorption and absorption characteristics, this can simplify thedetermination of the presence and characteristics of a coating.

The substrate can be a polymeric compound, optionally is a polyester, apolyolefin, a cyclic olefin copolymer, a COP, a polycarbonate, or acombination of these.

In the context of present invention, the coating characterized by theoutgassing method is typically a coating prepared by PECVD from, e.g.,an organosilicon precursor as described herein. For example, the coatingcan be a barrier layer, optionally is a SiO_(x) layer wherein x is fromabout 1.5 to about 2.9. For another example, the coating can be alubricity layer, characterized as defined in the Definition Sectionand/or a hydrophobic layer, characterized as defined in the DefinitionSection.

When the coating process whose product is inspected by the outgassingmethod is a PECVD coating performed under vacuum conditions, thesubsequent outgassing measurement can even be conducted without breakingthe vacuum used for PECVD.

The volatile species measured can be a volatile species released fromthe coating, a volatile species release from the substrate, or acombination of both. In one aspect, the volatile species is a volatilespecies released from the coating, optionally is a volatile coatingcomponent, and the inspection is performed to determine the presence,the properties and/or the composition of the coating. In another aspect,the volatile species is a volatile species released from the substrateand the inspection is performed to determine the presence of the coatingand/or the barrier effect of the coating.

The outgassing method of the present invention is for example suitableto determine the presence and characteristics of a coating on a vesselwall. Thus, the coated substrate can be a vessel having a wall which isat least partially coated on its inner or outer surface during thecoating process. For example, the coating is disposed on the innersurface of the vessel wall.

The conditions effective to distinguish the presence or absence of thecoating, and/or to determine a physical and/or chemical property of thecoating can include a test duration of less than one hour, or less thanone minute, or less than 50 seconds, or less than 40 seconds, or lessthan 30 seconds, or less than 20 seconds, or less than 15 seconds, orless than 10 seconds, or less than 8 seconds, or less than 6 seconds, orless than 4 seconds, or less than 3 seconds, or less than 2 seconds, orless than 1 second.

In order to increase the difference between the reference object and theinspection object with regard to the release rate and/or kind of themeasured volatile species, the release rate of the volatile species canbe modified by modifying the ambient pressure and/or temperature, and/orhumidity.

In an aspect, the outgassing is measured using a microcantilevermeasurement technique. E.g., the measuring can be carried out by

(i) (a) providing at least one microcantilever which has the property,when in the presence of an outgassed material, of moving or changing toa different shape;

(b) exposing the microcantilever to the outgassed material underconditions effective to cause the microcantilever to move or change to adifferent shape; and

(c) detecting the movement or different shape, optionally by reflectingan energetic incident beam, e.g. a laser beam, from a portion of themicrocantilever that changes shape, before and after exposing themicrocantilever to outgassing, and measuring the resulting deflection ofthe reflected beam at a point spaced from the cantilever; or by

(ii) (a) providing at least one microcantilever which resonates at adifferent frequency when in the presence of an outgassed material;

(b) exposing the microcantilever to the outgassed material underconditions effective to cause the microcantilever to resonate at adifferent frequency; and

(c) detecting the different resonant frequency, e.g. using a harmonicvibration sensor.

An apparatus for performing the outgassing method is also considered,for example an apparatus comprising a microcantilever as describedabove.

Using the outgassing method of the present invention, for example abarrier layer on a material that outgasses a vapor can be inspected,wherein the inspection method has several steps. A sample of basematerial that has at least a partial barrier layer is provided. In anaspect of the invention, the pressure is changed in the gas spaceadjacent to the coated surface. The outgassed gas passing through thebarrier layer is measured. If a pressure differential is present, themeasurement optionally is performed in the gas space adjacent to thecoated surface.

VII.E. Cuvettes

The PECVD coating methods, etc., described in this specification arealso useful for coating cuvettes to form a barrier layer, a hydrophobiclayer, a lubricity layer, or more than one of these. A cuvette is asmall tube of circular or square cross section, sealed at one end, madeof plastic, glass, or fused quartz (for UV light) and designed to holdsamples for spectroscopic experiments. The best cuvettes are as clear aspossible, without impurities that might affect a spectroscopic reading.Like a test tube or sample collection tube, a cuvette can be open to theatmosphere or have a cap to seal it shut. The PECVD-applied coatings ofthe present invention can be very thin, transparent, and optically flat,thus not interfering with optical testing of the cuvette or itscontents.

VII.F. Vials

The PECVD coating methods, etc., described in this specification arealso useful for coating vials to form a coating, for example a barrierlayer or a hydrophobic layer, or a combination of these layers. A vialis a small vessel or bottle, especially used to store medication asliquids, powders or lyophilized powders. They can also be sample vesselse.g. for use in autosampler devices in analytical chromatography. A vialcan have a tubular shape or a bottle-like shape with a neck. The bottomis usually flat unlike test tubes or sample collection tubes whichusually have a rounded bottom. Vials can be made, for example, ofplastic (e.g. polypropylene, COC, COP).

Computer-Readable Medium and Program Element

Furthermore, a computer-readable medium is provided, in which a computerprogram for coating and/or inspection of a vessel is stored which, whenbeing executed by a processor of a vessel processing system, causes theprocessor to perform the above or below mentioned method steps.

Furthermore, a program element for coating and/or inspection of a vesselis provided which, when being executed by a processor of a vesselprocessing system, causes the processor to carry out the above or belowmentioned method steps.

Other aspects of the invention will be apparent from this disclosure andthe accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram showing a vessel processing systemaccording to an embodiment of the disclosure.

FIG. 2 is a schematic sectional view of a vessel holder in a coatingstation according to an embodiment of the disclosure.

FIG. 3 is a view similar to FIG. 2 of an alternative embodiment of thedisclosure.

FIG. 4 is a diagrammatic plan view of an alternative embodiment of thevessel holder.

FIG. 5 is a diagrammatic plan view of another alternative embodiment ofthe vessel holder.

FIG. 6 is a view similar to FIG. 2 of vessel inspection apparatus.

FIG. 7 is a view similar to FIG. 2 of alternative vessel inspectionapparatus.

FIG. 8 is a section taken along section lines A-A of FIG. 2.

FIG. 9 is an alternative embodiment of the structure shown in FIG. 8.

FIG. 10 is a view similar to FIG. 2 of a vessel holder in a coatingstation according to another embodiment of the disclosure, employing aCCD detector.

FIG. 11 is a detail view similar to FIG. 10 of a light source anddetector that are reversed compared to the corresponding parts of FIG.6.

FIG. 12 is a view similar to FIG. 2 of a vessel holder in a coatingstation according to still another embodiment of the disclosure,employing microwave energy to generate the plasma.

FIG. 13 is a view similar to FIG. 2 of a vessel holder in a coatingstation according to yet another embodiment of the disclosure, in whichthe vessel can be seated on the vessel holder at the process station.

FIG. 14 is a view similar to FIG. 2 of a vessel holder in a coatingstation according to even another embodiment of the disclosure, in whichthe electrode can be configured as a coil.

FIG. 15 is a view similar to FIG. 2 of a vessel holder in a coatingstation according to another embodiment of the disclosure, employing atube transport to move a vessel to and from the coating station.

FIG. 16 is a diagrammatic view of the operation of a vessel transportsystem, such as the one shown in FIG. 15, to place and hold a vessel ina process station.

FIG. 17 is a diagrammatic view of a mold and mold cavity for forming avessel according to an aspect of the present disclosure.

FIG. 18 is a diagrammatic view of the mold cavity of FIG. 17 providedwith a vessel coating device according to an aspect of the presentdisclosure.

FIG. 19 is a view similar to FIG. 17 provided with an alternative vesselcoating device according to an aspect of the present disclosure.

FIG. 20 is an exploded longitudinal sectional view of a syringe and capadapted for use as a prefilled syringe.

FIG. 21 is a view generally similar to FIG. 2 showing a capped syringebarrel and vessel holder in a coating station according to an embodimentof the disclosure.

FIG. 22 is a view generally similar to FIG. 21 showing an uncappedsyringe barrel and vessel holder in a coating station according to yetanother embodiment of the invention.

FIG. 23 is a perspective view of a blood collection tube assembly havinga closure according to still another embodiment of the invention.

FIG. 24 is a fragmentary section of the blood collection tube andclosure assembly of FIG. 23.

FIG. 25 is an isolated section of an elastomeric insert of the closureof FIGS. 23 and 24.

FIG. 26 is a view similar to FIG. 22 of another embodiment of theinvention for processing syringe barrels and other vessels.

FIG. 27 is an enlarged detail view of the processing vessel of FIG. 26.

FIG. 28 is a schematic view of an alternative processing vessel.

FIG. 29 is a schematic view showing outgassing of a material through acoating.

FIG. 30 is a schematic sectional view of a test set-up for causingoutgassing of the wall of a vessel to the interior of the vessel andmeasurement of the outgassing using a measurement cell interposedbetween the vessel and a source of vacuum.

FIG. 31 is a plot of outgassing mass flow rate measured on thetest-set-up of FIG. 30 for multiple vessels.

FIG. 32 is a bar graph showing a statistical analysis of the endpointdata shown in FIG. 31.

FIG. 33 is a longitudinal section of a combined syringe barrel and gasreceiving volume according to another embodiment of the invention.

FIG. 34 is a view similar to FIG. 34 of another embodiment of theinvention including an electrode extension.

FIG. 35 is a view taken from section lines 35-35 of FIG. 34, showing thedistal gas supply openings and extension electrode of FIG. 34.

FIG. 36 is a perspective view of a double-walled blood collection tubeassembly according to still another embodiment of the invention.

FIG. 37 is a view similar to FIG. 22 showing another embodiment.

FIG. 38 is a view similar to FIG. 22 showing still another embodiment.

FIG. 39 is a view similar to FIG. 22 showing yet another embodiment.

FIG. 40 is a view similar to FIG. 22 showing even another embodiment.

FIG. 41 is a plan view of the embodiment of FIG. 40.

FIG. 42 is a fragmentary detail longitudinal section of an alternativesealing arrangement, usable for example, with the embodiments of FIGS.1, 2, 3, 6-10, 12-16, 18, 19, 33, and 37-41 for seating a vessel on avessel holder. FIG. 42 also shows an alternative syringe barrelconstruction usable, for example, with the embodiments of FIGS. 2, 3,6-10, 12-22, 26-28, 33-34, and 37-41.

FIG. 43 is a further enlarged detail view of the sealing arrangementshown in FIG. 42.

FIG. 44 is a view similar to FIG. 2 of an alternative gas deliverytube/inner electrode usable, for example with the embodiments of FIGS.1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33, 37-43, 46-49, and 52-54.

FIG. 45 is an alternative construction for a vessel holder usable, forexample, with the embodiments of FIGS. 1, 2, 3, 6-10, 12-16, 18, 19, 21,22, 26, 28, 33-35, and 37-44.

FIG. 46 is a schematic sectional view of an array of gas delivery tubesand a mechanism for inserting and removing the gas delivery tubes from avessel holder, showing a gas delivery tube in its fully advancedposition.

FIG. 47 is a view similar to FIG. 46, showing a gas delivery tube in anintermediate position.

FIG. 48 is a view similar to FIG. 46, showing a gas delivery tube in aretracted position. The array of gas delivery tubes of FIGS. 46-48 areusable, for example, with the embodiments of FIGS. 1, 2, 3, 8, 9, 12-16,18-19, 21-22, 26-28, 33-35, 37-45, 49, and 52-54. The mechanism of FIGS.46-48 is usable, for example, with the gas delivery tube embodiments ofFIGS. 2, 3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49, and52-54, as well as with the probes of the vessel inspection apparatus ofFIGS. 6 and 7.

FIG. 49 is a view similar to FIG. 16 showing a mechanism for deliveringvessels to be treated and a cleaning reactor to a PECVD coatingapparatus. The mechanism of FIG. 49 is usable with the vessel inspectionapparatus of FIGS. 1, 9, 15, and 16, for example.

FIG. 50 is an exploded view of a two-piece syringe barrel and Luer lockfitting. The syringe barrel is usable with the vessel treatment andinspection apparatus of FIGS. 1-22, 26-28, 33-35, 37-39, 44, and 53-54.

FIG. 51 is an assembled view of the two-piece syringe barrel and Luerlock fitting of FIG. 50.

FIG. 52 is a view similar to FIG. 42 showing a syringe barrel beingtreated that has no flange or finger stops 440. The syringe barrel isusable with the vessel treatment and inspection apparatus of FIGS. 1-19,27, 33, 35, 44-51, and 53-54.

FIG. 53 is a schematic view of an assembly for treating vessels. Theassembly is usable with the apparatus of FIGS. 1-3, 8-9, 12-16, 18-22,26-28, 33-35, and 37-49.

FIG. 54 is a diagrammatic view of the embodiment of FIG. 53.

FIG. 55 is a diagrammatic view similar to FIG. 2 of an embodiment of theinvention including a plasma screen.

FIG. 56 is a schematic sectional view of an array of gas delivery tubes,having independent gas supplies and a mechanism for inserting andremoving the gas delivery tubes from a vessel holder.

FIG. 57 is a plot of outgassing mass flow rate measured in Example 18.

FIG. 58 shows a linear rack, otherwise similar to FIG. 4.

FIG. 59 shows a schematic representation of a vessel processing systemaccording to an exemplary embodiment of the present invention.

FIG. 60 shows a schematic representation of a vessel processing systemaccording to another exemplary embodiment of the present invention.

FIG. 61 shows a processing station of a vessel processing systemaccording to an exemplary embodiment of the present invention.

FIG. 62 shows a portable vessel holder according to an exemplaryembodiment of the present invention.

The following reference characters are used in the drawing figures:

20 Vessel processing system 22 Injection molding machine 24 Visualinspection station 26 Inspection station (pre- coating) 28 Coatingstation 30 Inspection station (post- coating) 32 Optical sourcetransmission station (thickness) 34 Optical source transmission station(defects) 36 Output 38 Vessel holder 40 Vessel holder 42 Vessel holder44 Vessel holder 46 Vessel holder 48 Vessel holder 50 Vessel holder 52Vessel holder 54 Vessel holder 56 Vessel holder 58 Vessel holder 60Vessel holder 62 Vessel holder 64 Vessel holder 66 Vessel holder 68Vessel holder 70 Conveyor 72 Transfer mechanism (on) 74 Transfermechanism (off) 80 Vessel 82 Opening 84 Closed end 86 Wall 88 Interiorsurface 90 Barrier layer 92 Vessel port 94 Vacuum duct 96 Vacuum port 98Vacuum source 100 O-ring (of 92) 102 O-ring (of 96) 104 Gas inlet port106 O-ring (of 100) 108 Probe (counter electrode) 110 Gas delivery port(of 108) 112 Vessel holder (FIG. 3) 114 Housing (of 50 or 112) 116Collar 118 Exterior surface (of 80) 120 Vessel holder (array) 122 Vesselport (FIG. 4, 58) 130 Frame (FIG. 5) 132 Light source 134 Side channel136 Shut-off valve 138 Probe port 140 Vacuum port 142 PECVD gas inletport 144 PECVD gas source 146 Vacuum line (to 98) 148 Shut-off valve 150Flexible line (of 134) 152 Pressure gauge 154 Interior of vessel 80 160Electrode 162 Power supply 164 Sidewall (of 160) 166 Sidewall (of 160)168 Closed end (of 160) 170 Light source (FIG. 10) 172 Detector 174Pixel (of 172) 176 Interior surface (of 172) 182 Aperture (of 186) 184Wall (of 186) 186 Integrating sphere 190 Microwave power supply 192Waveguide 194 Microwave cavity 196 Gap 198 Top end (of 194) 200Electrode 202 Tube transport 204 Suction cup 208 Mold core 210 Moldcavity 212 Mold cavity liner 220 Bearing surface (FIG. 2) 222 Bearingsurface (FIG. 2) 224 Bearing surface (FIG. 2) 226 Bearing surface (FIG.2) 228 Bearing surface (FIG. 2) 230 Bearing surface (FIG. 2) 232 Bearingsurface (FIG. 2) 234 Bearing surface (FIG. 2) 236 Bearing surface (FIG.2) 238 Bearing surface (FIG. 2) 240 Bearing surface (FIG. 2) 250 Syringebarrel 252 Syringe 254 Interior surface (of 250) 256 Back end (of 250)258 Plunger (of 252) 260 Front end (of 250) 262 Cap 264 Interior surface(of 262) 266 Fitting 268 Vessel 270 Closure 272 Interior facing surface274 Lumen 276 Wall-contacting surface 278 Inner surface (of 280) 280Vessel wall 282 Stopper 284 Shield 286 Lubricity layer 288 Barrier layer290 Apparatus for coating, for example, 250 292 Inner surface (of 294)294 Restricted opening (of 250) 296 Processing vessel 298 Outer surface(of 250) 300 Lumen (of 250) 302 Larger opening (of 250) 304 Processingvessel lumen 306 Processing vessel opening 308 Inner electrode 310Interior passage (of 308) 312 Proximal end (of 308) 314 Distal end (of308) 316 Distal opening (of 308) 318 Plasma 320 Vessel support 322 Port(of 320) 324 Processing vessel (conduit type) 326 Vessel opening (of324) 328 Second opening (of 324) 330 Vacuum port (receiving 328) 332First fitting (male Luer taper) 334 Second fitting (female Luer taper)336 Locking collar (of 332) 338 First abutment (of 332) 340 Secondabutment (of 332) 342 O-ring 344 Dog 346 Wall 348 Coating (on 346) 350Permeation path 352 Vacuum 354 Gas molecule 355 Gas molecule 356Interface (between 346 and 348) 357 Gas molecule 358 PET vessel 359 Gasmolecule 360 Seal 362 Measurement cell 364 Vacuum pump 366 Arrows 368Conical passage 370 Bore 372 Bore 374 Chamber 376 Chamber 378 Diaphragm380 Diaphragm 382 Conductive surface 384 Conductive surface 386 Bypass390 Plot (glass tube) 392 Plot (PET uncoated) 394 Main plot (SiO₂coated) 396 Outliers (SiO₂ coated) 398 Inner electrode and gas supplytube 400 Distal opening 402 Extension counter electrode 404 Vent (FIG.7) 406 Valve 408 Inner wall (FIG. 36) 410 Outer wall (FIG. 36) 412Interior surface (FIG. 36) 414 Plate electrode (FIG. 37) 416 Plateelectrode (FIG. 37) 418 Vacuum conduit 420 Vessel holder 422 Vacuumchamber 424 Vessel holder 426 Counter electrode 428 Vessel holder (FIG.39) 430 Electrode assembly 432 Volume enclosed by 430 434 Pressureproportioning valve 436 Vacuum chamber conduit 438 Syringe barrel (FIG.42) 440 Flange (of 438) 442 Back opening (of 438) 444 Barrel wall (of438) 450 Vessel holder (FIG. 42) 452 Annular lip 454 Generallycylindrical sidewall (of 438) 456 Generally cylindrical inner surface(of 450) 458 Abutment 460 Pocket 462 O-ring 464 Outside wall (of 460)466 Bottom wall (of 460) 468 Top wall (of 460) 470 Inner electrode (FIG.44) 472 Distal portion (of 470) 474 Porous side wall (of 472) 476Internal passage (of 472) 478 Proximal portion (of 470) 480 Distal end(of 470) 482 Vessel holder body 484 Upper portion (of 482) 486 Baseportion (of 482) 488 Joint (between 484 and 486) 490 O-ring 492 Annularpocket 494 Radially extending abutment surface 496 Radially extendingwall 498 Screw 500 Screw 502 Vessel port 504 Second O-ring 506 Innerdiameter (of 490) 508 Vacuum duct (of 482) 510 Inner electrode 512 Innerelectrode 514 Insertion and removal mechanism 516 Flexible hose 518Flexible hose 520 Flexible hose 522 Valve 524 Valve 526 Valve 528Electrode cleaning station 530 Inner electrode drive 532 Cleaningreactor 534 Vent valve 536 Second gripper 538 Conveyer 539 Soluteretainer 540 Open end (of 532) 542 Interior space (of 532) 544 Syringe546 Plunger 548 Body 550 Barrel 552 Interior surface (of 550) 554Coating 556 Luer fitting 558 Luer taper 560 Internal passage (of 558)562 Internal surface 564 Coupling 566 Male part (of 564) 568 Female part(of 564) 570 Barrier layer 572 Locking collar 574 Main vacuum valve 576Vacuum line 578 Manual bypass valve 580 Bypass line 582 Vent valve 584Main reactant gas valve 586 Main reactant feed line 588 Organosiliconliquid reservoir 590 Organosilicon feed line (capillary) 592Organosilicon shut-off valve 594 Oxygen tank 596 Oxygen feed line 598Mass flow controller 600 Oxygen shut-off valve 602 Syringe exteriorbarrier layer 604 Lumen 606 Barrel exterior surface 610 Plasma screen612 Plasma screen cavity 614 Headspace 616 Pressure source 618 Pressureline 620 Capillary connection 630 Plots for uncoated COC 632 Plots forSiO_(x) coated COC 634 Plots for glass 5501 First processing station5502 Second processing station 5503 Third processing station 5504 Fourthprocessing station 5505 Processor 5506 User interface 5507 Bus 5701PECVD apparatus 5702 First detector 5703 Second detector 5704 Detector5705 Detector 5706 Detector 5707 Detector 7001 Conveyor exit branch 7002Conveyor exit branch 7003 Conveyor exit branch 7004 Conveyor exit branch

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will now be described more fully with reference tothe accompanying drawings, in which several embodiments are shown. Thisinvention can, however, be embodied in many different forms and shouldnot be construed as limited to the embodiments set forth here. Rather,these embodiments are examples of the invention, which has the fullscope indicated by the language of the claims. Like numbers refer tolike or corresponding elements throughout.

DEFINITION SECTION

In the context of the present invention, the following definitions andabbreviations are used:

RF is radio frequency; sccm is standard cubic centimeters per minute.

The term “at least” in the context of the present invention means “equalor more” than the integer following the term. The word “comprising” doesnot exclude other elements or steps, and the indefinite article “a” or“an” does not exclude a plurality unless indicated otherwise.

“First” and “second” or similar references to, e.g., processing stationsor processing devices refer to the minimum number of processing stationsor devices that are present, but do not necessarily represent the orderor total number of processing stations and devices. These terms do notlimit the number of processing stations or the particular processingcarried out at the respective stations.

For purposes of the present invention, an “organosilicon precursor” is acompound having at least one of the linkage:

which is a tetravalent silicon atom connected to an oxygen atom and anorganic carbon atom (an organic carbon atom being a carbon atom bondedto at least one hydrogen atom). A volatile organosilicon precursor,defined as such a precursor that can be supplied as a vapor in a PECVDapparatus, is an optional organosilicon precursor. Optionally, theorganosilicon precursor is selected from the group consisting of alinear siloxane, a monocyclic siloxane, a polycyclic siloxane, apolysilsesquioxane, an alkyl trimethoxysilane, a linear silazane, amonocyclic silazane, a polycyclic silazane, a polysilsesquiazane, and acombination of any two or more of these precursors.

In the context of the present invention, “essentially no oxygen” or(synonymously) “substantially no oxygen” is added to the gaseousreactant in some embodiments. This means that some residual atmosphericoxygen can be present in the reaction space, and residual oxygen fed ina previous step and not fully exhausted can be present in the reactionspace, which are defined here as essentially no oxygen present.Essentially no oxygen is present in the gaseous reactant if the gaseousreactant comprises less than 1 vol % O₂, for example less than 0.5 vol %O₂, and optionally is O₂-free. If no oxygen is added to the gaseousreactant, or if no oxygen at all is present during PECVD, this is alsowithin the scope of “essentially no oxygen.”

A “vessel” in the context of the present invention can be any type ofvessel with at least one opening and a wall defining an interiorsurface. The term “at least” in the context of the present inventionmeans “equal or more” than the integer following the term. Thus, avessel in the context of the present invention has one or more openings.One or two openings, like the openings of a sample tube (one opening) ora syringe barrel (two openings) are preferred. If the vessel has twoopenings, they can be of same or different size. If there is more thanone opening, one opening can be used for the gas inlet for a PECVDcoating method according to the present invention, while the otheropenings are either capped or open. A vessel according to the presentinvention can be a sample tube, e.g. for collecting or storingbiological fluids like blood or urine, a syringe (or a part thereof, forexample a syringe barrel) for storing or delivering a biologicallyactive compound or composition, e.g. a medicament or pharmaceuticalcomposition, a vial for storing biological materials or biologicallyactive compounds or compositions, a pipe, e.g. a catheter fortransporting biological materials or biologically active compounds orcompositions, or a cuvette for holding fluids, e.g. for holdingbiological materials or biologically active compounds or compositions.

A vessel can be of any shape, a vessel having a substantiallycylindrical wall adjacent to at least one of its open ends beingpreferred. Generally, the interior wall of the vessel is cylindricallyshaped, like, e.g. in a sample tube or a syringe barrel. Sample tubesand syringes or their parts (for example syringe barrels) arecontemplated.

A “hydrophobic layer” in the context of the present invention means thatthe coating lowers the wetting tension of a surface coated with thecoating, compared to the corresponding uncoated surface. Hydrophobicityis thus a function of both the uncoated substrate and the coating. Thesame applies with appropriate alterations for other contexts wherein theterm “hydrophobic” is used. The term “hydrophilic” means the opposite,i.e. that the wetting tension is increased compared to reference sample.The present hydrophobic layers are primarily defined by theirhydrophobicity and the process conditions providing hydrophobicity, andoptionally can have a composition according to the empirical compositionor sum formula Si_(w)O_(x)C_(y)H_(z), for example where w is 1, x isfrom about 0.5 to about 2.4, y is from about 0.6 to about 3, and z isfrom about 2 to about 9, optionally where w is 1, x is from about 0.5 to1, y is from about 2 to about 3, and z is from 6 to about 9. Thesevalues of w, x, y, and z are applicable to the empirical compositionSi_(w)O_(x)C_(y)H_(z) throughout this specification. The values of w, x,y, and z used throughout this specification should be understood asratios or an empirical formula (e.g. for a coating), rather than as alimit on the number or type of atoms in a molecule. For example,octamethylcyclotetrasiloxane, which has the molecular compositionSi₄O₄C₈H₂₄, can be described by the following empirical formula, arrivedat by dividing each of w, x, y, and z in the molecular formula by 4, thelargest common factor: Si₁O₁C₂H₆. The values of w, x, y, and z are alsonot limited to integers. For example, (acyclic) octamethyltrisiloxane,molecular composition Si₃O₂C₈H₂₄, is reducible to Si₁O_(0.67)C₂H₈.

“Wetting tension” is a specific measure for the hydrophobicity orhydrophilicity of a surface. An optional wetting tension measurementmethod in the context of the present invention is ASTM D 2578 or amodification of the method described in ASTM D 2578. This method usesstandard wetting tension solutions (called dyne solutions) to determinethe solution that comes nearest to wetting a plastic film surface forexactly two seconds. This is the film's wetting tension. The procedureutilized is varied herein from ASTM D 2578 in that the substrates arenot flat plastic films, but are tubes made according to the Protocol forForming PET Tube and (except for controls) coated according to theProtocol for Coating Tube Interior with Hydrophobic Layer (see Example9).

A “lubricity layer” according to the present invention is a coatingwhich has a lower frictional resistance than the uncoated surface. Inother words, it reduces the frictional resistance of the coated surfacein comparison to a reference surface which is uncoated. The presentlubricity layers are primarily defined by their lower frictionalresistance than the uncoated surface and the process conditionsproviding lower frictional resistance than the uncoated surface, andoptionally can have a composition according to the empirical compositionSi_(w)O_(x)C_(y)H_(z), as defined in this Definition Section.“Frictional resistance” can be static frictional resistance and/orkinetic frictional resistance. One of the optional embodiments of thepresent invention is a syringe part, e.g. a syringe barrel or plunger,coated with a lubricity layer. In this contemplated embodiment, therelevant static frictional resistance in the context of the presentinvention is the breakout force as defined herein, and the relevantkinetic frictional resistance in the context of the present invention isthe plunger sliding force as defined herein. For example, the plungersliding force as defined and determined herein is suitable to determinethe presence or absence and the lubricity characteristics of a lubricitylayer in the context of the present invention whenever the coating isapplied to any syringe or syringe part, for example to the inner wall ofa syringe barrel. The breakout force is of particular relevance forevaluation of the coating effect on a prefilled syringe, i.e. a syringewhich is filled after coating and can be stored for some time, e.g.several months or even years, before the plunger is moved again (has tobe “broken out”).

The “plunger sliding force” in the context of the present invention isthe force required to maintain movement of a plunger in a syringebarrel, e.g. during aspiration or dispense. It can advantageously bedetermined using the ISO 7886-1:1993 test described herein and known inthe art. A synonym for “plunger sliding force” often used in the art is“plunger force” or “pushing force”.

The “breakout force” in the context of the present invention is theinitial force required to move the plunger in a syringe, for example ina prefilled syringe.

Both “plunger sliding force” and “breakout force” and methods for theirmeasurement are described in more detail in subsequent parts of thisdescription.

“Slidably” means that the plunger is permitted to slide in a syringebarrel.

In the context of this invention, “substantially rigid” means that theassembled components (ports, duct, and housing, explained further below)can be moved as a unit by handling the housing, without significantdisplacement of any of the assembled components respecting the others.Specifically, none of the components are connected by hoses or the likethat allow substantial relative movement among the parts in normal use.The provision of a substantially rigid relation of these parts allowsthe location of the vessel seated on the vessel holder to be nearly aswell known and precise as the locations of these parts secured to thehousing.

In the following, the apparatus for performing the present inventionwill be described first, followed by the coating methods, coatings andcoated vessels, and the uses according to the present invention.

I. Vessel Processing System Having Multiple Processing Stations andMultiple Vessel Holders

I. A vessel processing system is contemplated comprising a firstprocessing station, a second processing station, a multiplicity ofvessel holders, and a conveyor. The first processing station isconfigured for processing a vessel having an opening and a wall definingan interior surface. The second processing station is spaced from thefirst processing station and configured for processing a vessel havingan opening and a wall defining an interior surface.

I. At least some, optionally all, of the vessel holders include a vesselport configured to receive and seat the opening of a vessel forprocessing the interior surface of a seated vessel via the vessel portat the first processing station. The conveyor is configured fortransporting a series of the vessel holders and seated vessels from thefirst processing station to the second processing station for processingthe interior surface of a seated vessel via the vessel port at thesecond processing station.

I. Referring first to FIG. 1, a vessel processing system generallyindicated as 20 is shown. The vessel processing system can includeprocessing stations which more broadly are contemplated to be processingdevices. The vessel processing system 20 of the illustrated embodimentcan include an injection molding machine 22 (which can be regarded as aprocessing station or device), additional processing stations or devices24, 26, 28, 30, 32, and 34, and an output 36 (which can be regarded as aprocessing station or device). At a minimum, the system 20 has at leasta first processing station, for example station 28, and a secondprocessing station, for example 30, 32, or 34.

I. Any of the processing stations 22-36 in the illustrated embodimentcan be a first processing station, any other processing station can be asecond processing station, and so forth.

I. The embodiment illustrated in FIG. 1 can include eight processingstations or devices: 22, 24, 26, 28, 30, 32, 34, and 36. The exemplaryvessel processing system 20 includes an injection molding machine 22, apost-molding inspection station 24, a pre-coating inspection station 26,a coating station 28, a post-coating inspection station 30, an opticalsource transmission station 32 to determine the thickness of thecoating, an optical source transmission station 34 to examine thecoating for defects, and an output station 36.

I. The system 20 can include a transfer mechanism 72 for moving vesselsfrom the injection molding machine 22 to a vessel holder 38. Thetransfer mechanism 72 can be configured, for example, as a robotic armthat locates, moves to, grips, transfers, orients, seats, and releasesthe vessels 80 to remove them from the vessel forming machine 22 andinstall them on the vessel holders such as 38.

I. The system 20 also can include a transfer mechanism at a processingstation 74 for removing the vessel from one or more vessel holders suchas 66, following processing the interior surface of the seated vesselsuch as 80 (FIG. 1). The vessels 80 are thus movable from the vesselholder 66 to packaging, storage, or another appropriate area or processstep, generally indicated as 36. The transfer mechanism 74 can beconfigured, for example, as a robotic arm that locates, moves to, grips,transfers, orients, places, and releases the vessels 80 to remove themfrom the vessel holders such as 38 and place them on other equipment atthe station 36.

I. The processing stations or devices 32, 34, and 36 shown in FIG. 1optionally carry out one or more appropriate steps downstream of thecoating and inspection system 20, after the individual vessels 80 areremoved from the vessel holders such as 64. Some non-limiting examplesof functions of the stations or devices 32, 34, and 36 include:

-   -   placing the treated and inspected vessels 80 on a conveyor to        further processing apparatus;    -   adding chemicals to the vessels;    -   capping the vessels;    -   placing the vessels in suitable processing racks;    -   packaging the vessels; and    -   sterilizing the packaged vessels.

I. The vessel processing system 20 as illustrated in FIG. 1 also caninclude a multiplicity of vessel holders (or “pucks,” as they can insome embodiments resemble a hockey puck) respectively 38 through 68, anda conveyor generally indicated as an endless band 70 for transportingone or more of the vessel holders 38-68, and thus vessels such as 80, toor from the processing stations 22, 24, 26, 28, 30, 32, 34, and 36.

I. The processing station or device 22 can be a device for forming thevessels 80. One contemplated device 22 can be an injection moldingmachine. Another contemplated device 22 can be a blow molding machine.Vacuum molding machines, draw molding machines, cutting or millingmachines, glass drawing machines for glass or other draw-formablematerials, or other types of vessel forming machines are alsocontemplated. Optionally, the vessel forming station 22 can be omitted,as vessels can be obtained already formed.

II. Vessel Holders

II.A. The portable vessel holders 38-68 are provided for holding andconveying a vessel having an opening while the vessel is processed. Thevessel holder includes a vessel port, a second port, a duct, and aconveyable housing.

II.A. The vessel port is configured to seat a vessel opening in amutually communicating relation. The second port is configured toreceive an outside gas supply or vent. The duct is configured forpassing one or more gases between a vessel opening seated on the vesselport and the second port. The vessel port, second port, and duct areattached in substantially rigid relation to the conveyable housing.Optionally, the portable vessel holder weighs less than five pounds. Anadvantage of a lightweight vessel holder is that it can more readily betransported from one processing station to another.

II.A. In certain embodiments of the vessel holder the duct morespecifically is a vacuum duct and the second port more specifically is avacuum port. The vacuum duct is configured for withdrawing a gas via thevessel port from a vessel seated on the vessel port. The vacuum port isconfigured for communicating between the vacuum duct and an outsidesource of vacuum. The vessel port, vacuum duct, and vacuum port can beattached in substantially rigid relation to the conveyable housing.

II.A. The vessel holders of embodiments II.A. and II.A.1. are shown, forexample, in FIG. 2. The vessel holder 50 has a vessel port 82 configuredto receive and seat the opening of a vessel 80. The interior surface ofa seated vessel 80 can be processed via the vessel port 82. The vesselholder 50 can include a duct, for example a vacuum duct 94, forwithdrawing a gas from a vessel 80 seated on the vessel port 92. Thevessel holder can include a second port, for example a vacuum port 96communicating between the vacuum duct 94 and an outside source ofvacuum, such as the vacuum pump 98. The vessel port 92 and vacuum port96 can have sealing elements, for example O-ring butt seals,respectively 100 and 102, or side seals between an inner or outercylindrical wall of the vessel port 82 and an inner or outer cylindricalwall of the vessel 80 to receive and form a seal with the vessel 80 oroutside source of vacuum 98 while allowing communication through theport. Gaskets or other sealing arrangements can or also be used.

II.A. The vessel holder such as 50 can be made of any material, forexample thermoplastic material and/or electrically nonconductivematerial. Or, the vessel holder such as 50 can be made partially, oreven primarily, of electrically conductive material and faced withelectrically nonconductive material, for example in the passages definedby the vessel port 92, vacuum duct 94, and vacuum port 96. Examples ofsuitable materials for the vessel holder 50 are: a polyacetal, forexample Delrin® acetal material sold by E.I. du Pont De Nemours andCompany, Wilmington Del.; polytetrafluoroethylene (PTFE), for exampleTeflon® PTFE sold by E.I. du Pont De Nemours and Company, WilmingtonDel.; Ultra-High-Molecular-Weight Polyethylene (UHMWPE); High densityPolyethylene (HDPE); or other materials known in the art or newlydiscovered.

II.A. FIG. 2 also illustrates that the vessel holder, for example 50,can have a collar 116 for centering the vessel 80 when it is approachingor seated on the port 92.

Array of Vessel Holders

II.A. Yet another approach to treat, inspect, and/or move parts througha production system can be to use an array of vessel holders. The arraycan be comprised of individual pucks or be a solid array into which thedevices are loaded. An array can allow more than one device, optionallymany devices, to be tested, conveyed or treated/coated simultaneously.The array can be one-dimensional, for example grouped together to form alinear rack, or two-dimensional, similar to a tub or tray.

II.A. FIGS. 4, 5, and 58 show three array approaches. FIG. 4 shows asolid array 120 into (or onto) which the devices or vessels 80 areloaded. In this case, the devices or vessels 80 can move through theproduction process as a solid array, although they can be removed duringthe production process and transferred to individual vessel holders. Asingle vessel holder 120 has multiple vessel ports such as 122 forconveying an array of seated vessels such as 80, moving as a unit. Inthis embodiment, multiple individual vacuum ports such as 96 can beprovided to receive an array of vacuum sources 98. Or, a single vacuumport connected to all the vessel ports such as 96 can be provided.Multiple gas inlet probes such as 108 can also be provided in an array.The arrays of gas inlet probes or vacuum sources can be mounted to moveas a unit to process many vessels such as 80 simultaneously. Or, themultiple vessel ports such as 122 can be addressed one or more rows at atime, or individually, in a processing station. The number of devices inthe array can be related to the number of devices that are molded in asingle step or to other tests or steps that can allow for efficiencyduring the operation. In the case of treating/coating an array, theelectrodes can either be coupled together (to form one large electrode),or can be individual electrodes each with its own power supply. All ofthe above approaches can still be applicable (from the standpoint of theelectrode geometry, frequency etc.).

II.A. In FIG. 5, individual pucks or vessel holders (as discussed above)are brought together into an array, as by surrounding them with anexternal frame 130. This arrangement provides the advantages of thesolid array of FIG. 4, when that is desired, and also allows the arrayto be disassembled for other processing steps in which the vessels 80are addressed in different arrays or singly.

II.A. FIG. 58 shows a linear rack, otherwise similar to FIG. 4. If alinear rack is used, another option, in addition to those explainedabove, is to transport the rack in single file fashion through aprocessing station, processing the vessels serially.

II.B. Vessel Holder Including O-ring Arrangement

II.B. FIGS. 42 and 43 are respectively a fragmentary detail longitudinalsection and a detail view of a vessel holder 450 provided with analternative sealing arrangement, usable for example, with the vesselholder embodiments of FIGS. 2, 3, 6, 7, 19, 12, 13, 16, 18, 19, 30, and43 for seating a vessel on a vessel holder. Referring to FIG. 42, thevessel, for example a syringe barrel 438, seated on the vessel holder450 has a back opening 442 defined by a generally annular (and commonlychamfered or rounded) lip 452, as well as a generally cylindricalsidewall 454. A medical fluid collection tube commonly has the same typeof lip 452, but without a flange 440, and thus can be seated on thevessel holder 450 instead.

II.B. The vessel holder 450 in the embodiment as illustrated includes agenerally cylindrical inner surface 456 that in the illustratedembodiment serves as a guide surface to receive the generallycylindrical sidewall 454 of the syringe barrel 438. The well is furtherdefined by a generally annular abutment 458 against which the annularlip 452 abuts when the syringe barrel 438 is seated on the vessel holder450. A generally annular pocket or groove 460 formed in the innersurface 456 is provided for retaining the sealing element, for examplean O-ring 462. The radial depth of the pocket 460 is less than theradial cross-section of the sealing element, for example an O-ring 462(as illustrated in FIG. 42), and the inner diameter of the O-ring 462optionally is optionally slightly smaller than the outer diameter of theannular lip 452.

II.B. These relative dimensions cause the radial cross-section of theO-ring 462 to compress horizontally between at least the outside wall464 of the pocket 460 and the generally cylindrical sidewall 454 of thesyringe barrel 438, as shown in FIG. 42, when a vessel such as 438 isseated as shown in FIG. 42. This compression flattens the bearingsurfaces of the O-ring 462, forming a seal between at least the outsidewall 464 of the pocket 460 and the generally cylindrical sidewall 454 ofthe syringe barrel 438.

II.B. The pocket 460 optionally can be constructed, in relation to thedimensions of the O-ring 462, to form two more seals between the bottomand top walls 466 and 468 and the sidewall 454, by spacing the top andbottom walls 468 and 466 about as far apart as the corresponding radialcross-section diameter of the O-ring 462. When the O-ring 462 issqueezed between the outside wall 464 and the generally cylindricalsidewall 454 of the pocket 460, its resilience will cause it to expandupward and downward as shown in FIG. 43, thus also engaging the top andbottom walls 466 and 464 and flattening against them. The O-ring 462optionally will thus be deformed both vertically and horizontally,tending to square its normally round cross-section. Additionally, theannular lip 452 seated on the abutment 458 will limit the flow of PECVDprocess reactants and other gases and materials introduced through oradjacent to the back opening 442.

II.B. As a result of this optional construction, only the gap at thelower right corner of the O-ring 462, as shown in FIG. 43, is outsidethe O-rings and thus exposed to process gases, plasma, etc. introducedto or generated in the interior of the vessel 438. This constructionprotects the O-ring 462 and the adjacent surfaces (as of the outsidesurface of the sidewall 438) from unwanted build-up of PECVD depositsand attack by the activated chemical species in the plasma.Additionally, the vessel 438 is more positively located by the hardsurface of the abutment 458, as opposed to the resilient surface thatwould be presented by a butt seat of the annular lip 452 directlyagainst the O-ring as illustrated in some of the other Figures. Further,the forces on the respective portions around the major circumference ofthe O-ring 462 are more evenly distributed, as the vessel 438 isconstrained against any substantial rocking.

II.B. Or, the pocket 460 can be formed with its bottom wall 466 abovethe abutment 458 shown in FIG. 43. In another embodiment, more than oneaxially spaced pocket 460 can be provided to provide a double orhigher-level seal and to further restrain the vessel 438 against rockingwhen seated against the abutment 458.

II.B. FIG. 45 is an alternative construction for a vessel holder 482usable, for example, with the embodiments of FIGS. 1, 2, 3, 6-10, 12-16,18, 19, 21, 22, 26, 28, 33-35, and 37-44. The vessel holder 482comprises an upper portion 484 and a base 486 joined together at a joint488. A sealing element, for example an O-ring 490 (the right side ofwhich is cut away to allow the pocket retaining it to be described) iscaptured between the upper portion 484 and the base 486 at the joint488. In the illustrated embodiment, the O-ring 490 is received in anannular pocket 492 to locate the O-ring when the upper portion 484 isjoined to the base 486.

II.B. In this embodiment, the O-ring 490 is captured and bears against aradially extending abutment surface 494 and the radially extending wall496 partially defining the pocket 492 when the upper portion 484 and thebase 486 are joined, in this case by the screws 498 and 500. The O-ring490 thus seats between the upper portion 484 and base 486. The O-ring490 captured between the upper portion 484 and the base 486 alsoreceives the vessel 80 (removed in this figure for clarity ofillustration of other features) and forms a first O-ring seal of thevessel port 502 about the vessel 80 opening, analogous to the O-ringseal arrangement about the vessel back opening 442 in FIG. 42.

II.B. In this embodiment, though not a requirement, the vessel port 502has both the first O-ring 490 seal and a second axially spaced O-ring504 seal, each having an inner diameter such as 506 sized to receive theouter diameter (analogous to the sidewall 454 in FIG. 43) of a vesselsuch as 80 for sealing between the vessel port 502 and a vessel such as80. The spacing between the O-rings 490 and 504 provides support for avessel such as 80 at two axially spaced points, preventing the vesselsuch as 80 from being skewed with respect to the O-rings 490 and 504 orthe vessel port 502. In this embodiment, though not a requirement, theradially extending abutment surface 494 is located proximal of theO-ring 490 and 506 seals and surrounding the vacuum duct 508.

III. Methods for Transporting Vessels—Processing Vessels Seated onVessel Holders

III.A. Transporting Vessel Holders to Processing Stations

III.A. FIGS. 1, 2, and 10 show a method for processing a vessel 80. Themethod can be carried out as follows.

III.A. A vessel 80 can be provided having an opening 82 and a wall 86defining an interior surface 88. As one embodiment, the vessel 80 can beformed in and then removed from a mold such as 22. Optionally within 60seconds, or within 30 seconds, or within 25 seconds, or within 20seconds, or within 15 seconds, or within 10 seconds, or within 5seconds, or within 3 seconds, or within 1 second after removing thevessel from the mold, or as soon as the vessel 80 can be moved withoutdistorting it during processing (assuming that it is made at an elevatedtemperature, from which it progressively cools), the vessel opening 82can be seated on the vessel port 92. Quickly moving the vessel 80 fromthe mold 22 to the vessel port 92 reduces the dust or other impuritiesthat can reach the surface 88 and occlude or prevent adhesion of thebarrier or other type of coating 90. Also, the sooner a vacuum is drawnon the vessel 80 after it is made, the less chance any particulateimpurities have of adhering to the interior surface 88.

III.A. A vessel holder such as 50 comprising a vessel port 92 can beprovided. The opening 82 of the vessel 80 can be seated on the vesselport 92. Before, during, or after seating the opening 82 of the vessel80 on the vessel port 92, the vessel holder such as 40 (for example inFIG. 6) can be transported into engagement with one or more of thebearing surfaces 220-240 to position the vessel holder 40 with respectto the processing device or station such as 24.

III.A. One, more than one, or all of the processing stations such as24-34, as illustrated by the station 24 shown in FIG. 6, can include abearing surface, such as one or more of the bearing surfaces 220, 222,224, 226, 228, 230, 232, 234, 236, 238, or 240, for supporting one ormore vessel holders such as 40 in a predetermined position whileprocessing the interior surface 88 of the seated vessel 80 at theprocessing station or device such as 24. These bearing surfaces can bepart of stationary or moving structure, for example tracks or guidesthat guide and position the vessel holder such as 40 while the vessel isbeing processed. For example, the downward-facing bearing surfaces 222and 224 locate the vessel holder 40 and act as a reaction surface toprevent the vessel holder 40 from moving upward when the probe 108 isbeing inserted into the vessel holder 40. The reaction surface 236locates the vessel holder and prevents the vessel holder 40 from movingto the left while a vacuum source 98 (per FIG. 2) is seated on thevacuum port 96. The bearing surfaces 220, 226, 228, 232, 238, and 240similarly locate the vessel holder 40 and prevent horizontal movementduring processing. The bearing surfaces 230 and 234 similarly locate thevessel holder such as 40 and prevent it from moving vertically out ofposition. Thus, a first bearing surface, a second bearing surface, athird bearing surface, or more can be provided at each of the processingstations such as 24-34.

III.A. The interior surface 88 of the seated vessel 80 can be thenprocessed via the vessel port 92 at the first processing station, whichcan be, as one example, the barrier application or other type of coatingstation 28 shown in FIG. 2. The vessel holder 50 and seated vessel 80are transported from the first processing station 28 to the secondprocessing station, for example the processing station 32. The interiorsurface 88 of the seated vessel 80 can be processed via the vessel port92 at the second processing station such as 32.

III.A. Any of the above methods can include the further step of removingthe vessel 80 from the vessel holder such as 66 following processing theinterior surface 88 of the seated vessel 80 at the second processingstation or device.

III.A. Any of the above methods can include the further step, after theremoving step, of providing a second vessel 80 having an opening 82 anda wall 86 defining an interior surface 88. The opening 82 of the secondvessel such as 80 can be seated on the vessel port 92 of another vesselholder such as 38. The interior surface of the seated second vessel 80can be processed via the vessel port 92 at the first processing stationor device such as 24. The vessel holder such as 38 and seated secondvessel 80 can be transported from the first processing station or device24 to the second processing station or device such as 26. The seatedsecond vessel 80 can be processed via the vessel port 92 by the secondprocessing station or device 26.

III.B. Transporting Processing Devices to Vessel Holders or Vice Versa.

III.B. Or, the processing stations can more broadly be processingdevices, and either the vessel holders can be conveyed relative to theprocessing devices, the processing devices can be conveyed relative tothe vessel holders, or some of each arrangement can be provided in agiven system. In still another arrangement, the vessel holders can beconveyed to one or more stations, and more than one processing devicecan be deployed at or near at least one of the stations. Thus, there isnot necessarily a one-to-one correspondence between the processingdevices and processing stations.

III.B. A method including several parts is contemplated for processing avessel. A first processing device such as the probe 108 (FIG. 2) and asecond processing device such as a light source 170 (FIG. 10) areprovided for processing vessels such as 80. A vessel 80 is providedhaving an opening 82 and a wall 86 defining an interior surface 88. Avessel holder 50 is provided comprising a vessel port 92. The opening 82of the vessel 80 is seated on the vessel port 92.

III.B. The first processing device such as the probe 108 is moved intooperative engagement with the vessel holder 50, or vice versa. Theinterior surface 88 of the seated vessel 80 is processed via the vesselport 92 using the first processing device or probe 108.

III.B. The second processing device such as 170 (FIG. 10) is then movedinto operative engagement with the vessel holder 50, or vice versa. Theinterior surface 88 of the seated vessel 80 is processed via the vesselport 92 using the second processing device such as the light source 170.

III.B. Optionally, any number of additional processing steps can beprovided. For example, a third processing device 34 can be provided forprocessing vessels 80. The third processing device 34 can be moved intooperative engagement with the vessel holder 50, or vice versa. Theinterior surface of the seated vessel 80 can be processed via the vesselport 92 using the third processing device 34.

III.B. In another method for processing a vessel, the vessel 80 can beprovided having an opening 82 and a wall 86 defining an interior surface88. A vessel holder such as 50 comprising a vessel port 92 can beprovided. The opening 82 of the vessel 80 can be seated on the vesselport 92. The interior surface 88 of the seated vessel 80 can beprocessed via the vessel port 92 at by the first processing device,which can be, as one example, the barrier or other type of coatingdevice 28 shown in FIG. 2. The vessel holder 50 and seated vessel 80 aretransported from the first processing device 28 to the second processingdevice, for example the processing device 34 shown in FIGS. 1 and 10.The interior surface 88 of the seated vessel 80 can be then processedvia the vessel port 92 by the second processing device such as 34.

III.C. Using Gripper for Transporting Tube to and from Coating Station

III.C. Yet another embodiment is a method of PECVD treatment of a firstvessel, including several steps. A first vessel is provided having anopen end, a closed end, and an interior surface. At least a firstgripper is configured for selectively holding and releasing the closedend of the first vessel. The closed end of the first vessel is grippedwith the first gripper and, using the first gripper, transported to thevicinity of a vessel holder configured for seating to the open end ofthe first vessel. The first gripper is then used to axially advance thefirst vessel and seat its open end on the vessel holder, establishingsealed communication between the vessel holder and the interior of thefirst vessel.

III.C. At least one gaseous reactant is introduced within the firstvessel through the vessel holder. Plasma is formed within the firstvessel under conditions effective to form a reaction product of thereactant on the interior surface of the first vessel.

III.C. The first vessel is then unseated from the vessel holder and,using the first gripper or another gripper, the first vessel is axiallytransported away from the vessel holder. The first vessel is thenreleased from the gripper used to axially transport it away from thevessel holder.

III.C. Referring again to FIGS. 16 and 49, a series conveyor 538 can beused to support and transport multiple grippers such as 204 through theapparatus and process as described here. The grippers 204 areoperatively connected to the series conveyor 538 and configured forsuccessively transporting a series of at least two vessels 80 to thevicinity of the vessel holder 48 and carrying out the other steps of thecleaning method as described here.

IV. PECVD Apparatus for Making Vessels

IV.A. PECVD Apparatus Including Vessel Holder, Internal Electrode,Vessel as Reaction Chamber

IV.A. Another embodiment is a PECVD apparatus including a vessel holder,an inner electrode, an outer electrode, and a power supply. A vesselseated on the vessel holder defines a plasma reaction chamber, whichoptionally can be a vacuum chamber. Optionally, a source of vacuum, areactant gas source, a gas feed or a combination of two or more of thesecan be supplied. Optionally, a gas drain, not necessarily including asource of vacuum, is provided to transfer gas to or from the interior ofa vessel seated on the port to define a closed chamber.

IV.A. The PECVD apparatus can be used for atmospheric-pressure PECVD, inwhich case the plasma reaction chamber does not need to function as avacuum chamber.

IV.A. In the embodiment illustrated in FIG. 2, the vessel holder 50comprises a gas inlet port 104 for conveying a gas into a vessel seatedon the vessel port. The gas inlet port 104 has a sliding seal providedby at least one O-ring 106, or two O-rings in series, or three O-ringsin series, which can seat against a cylindrical probe 108 when the probe108 is inserted through the gas inlet port 104. The probe 108 can be agas inlet conduit that extends to a gas delivery port at its distal end110. The distal end 110 of the illustrated embodiment can be inserteddeep into the vessel 80 for providing one or more PECVD reactants andother process gases.

IV.A. Optionally in the embodiment illustrated in FIG. 2, or moregenerally in any embodiment disclosed, such as the embodiments of FIG.1-5, 8, 9, 12-16, 18, 19, 21, 22, 26-28, 33-35, 37-49, or 52-55, and asspecifically disclosed in FIG. 55, a plasma screen 610 can be providedto confine the plasma formed within the vessel 80 generally to thevolume above the plasma screen 610. The plasma screen 610 is aconductive, porous material, several examples of which are steel wool,porous sintered metal or ceramic material coated with conductivematerial, or a foraminous plate or disk made of metal (for examplebrass) or other conductive material. An example is a pair of metal diskshaving central holes sized to pass the gas inlet 108 and having0.02-inch (0.5 mm) diameter holes spaced 0.04 inches (1 mm) apart,center-to-center, the holes providing 22% open area as a proportion ofthe surface area of the disk.

IV.A. The plasma screen 610, for example for embodiments in which theprobe 108 also functions as an counter electrode, can make intimateelectrical contact with the gas inlet 108 at or near the opening 82 ofthe tube, syringe barrel, or other vessel 80 being processed.Alternatively, the plasma screen 610 can be grounded, optionally havinga common potential with the gas inlet 108. The plasma screen 610 reducesor eliminates the plasma in the vessel holder 50 and its internalpassages and connections, for example the vacuum duct 94, the gas inletport 104, the vicinity of the O-ring 106, the vacuum port 96, the O-ring102, and other apparatus adjacent to the gas inlet 108. At the sametime, the porosity of the plasma screen allows process gases, air, andthe like to flow out of the vessel 80 into the vacuum port 96 anddownstream apparatus.

IV.A. In the coating station 28 illustrated in FIG. 3, the vessel holder112 comprises a composite gas inlet port and vacuum port 96communicating with the vessel port 92, respectively for conveying a gasinto a vessel 80 seated on the vessel port 92 (via the probe 108) andwithdrawing a gas from a vessel seated on the vessel port 92 (via thevacuum source 98). In this embodiment, the gas inlet probe 108 andvacuum source 98 can be provided as a composite probe. The two probescan be advanced as a unit or separately, as desired. This arrangementeliminates the need for a third seal 106 and allows the use of buttseals throughout. A butt seal allows the application of an axial force,for example by drawing a vacuum within the vessel 80, to positively seatthe vessel 80 and vacuum source 98 by deforming the O-rings, tending toclose any gap left by the presence of any irregularities in the sealingsurface on either side of the O-ring. In the embodiment of FIG. 3, theaxial forces applied by the vessel 80 and vacuum source 98 on the vesselholder 112 are in opposition, tending to hold the vessel 80 and thevessel holder 112 together and maintain the respective butt seals.

IV.A. FIG. 13 is a view similar to FIG. 2 of a vessel holder 48 in acoating station according to yet another embodiment of the disclosure,in which the vessel 80 can be seated on the vessel holder 48 at theprocess station. This can be used to process a vessel 80 that does nottravel with a vessel holder such as 48, or it can be used in a barrieror other type of coating station 28 that first seats the vessel 80 in avessel holder such as 48 before the seated vessel 80 is conveyed toother apparatus by the system 20.

IV.A. FIG. 13 shows a cylindrical electrode 160 suited for frequenciesfrom 50 Hz to 1 GHz, as an alternative to the U-shaped electrode ofFIGS. 2 and 9. The vessel holder (or the electrode) can be moved intoplace prior to activation by either moving the electrode down or thevessel holder up. Or, the movement of the vessel holder and electrode inthe vertical plane can be circumvented by creating an electrode 160constructed like a clamshell (two half cylinders that can come togetherfrom opposite sides when the vessel holder is in position and ready fortreatment/coating). IV.A. Optionally, at the coating station 28 thevacuum source 98 makes a seal with the puck or vessel holder 50 that canbe maintained during movement of the vessel holder, if the process is acontinuous process in which the tube is moved through the coatingstation such as 28 while a vacuum is drawn and gas is introduced throughthe probe 108. Or, a stationary process can be employed in which thepuck or vessel holder 50 is moved into a stationary position, at whichtime the probe 108 is pushed up into the device and then the pump orvacuum source 98 is coupled at the vacuum port 96 and activated tocreate a vacuum. Once the probe 108 is in place and the vacuum created,plasma can be established inside of the tube or vessel 80 with anexternal fixed electrode 160 that is independent of the puck or vesselholder 50 and the tube or other vessel 80.

IV.A. FIG. 53 shows additional optional details of the coating station28 that are usable, for example, with the embodiments of FIGS. 1, 2, 3,6-10, 12-16, 18, 19, 21, 22, 26-28, 30, 33-35, 37-44, and 52. Thecoating station 28 can also have a main vacuum valve 574 in its vacuumline 576 leading to the pressure sensor 152. A manual bypass valve 578is provided in the bypass line 580. A vent valve 582 controls flow atthe vent 404.

IV.A. Flow out of the PECVD gas source 144 is controlled by a mainreactant gas valve 584 regulating flow through the main reactant feedline 586. One component of the gas source 144 is the organosiliconliquid reservoir 588. The contents of the reservoir 588 are drawnthrough the organosilicon capillary line 590, which is provided at asuitable length to provide the desired flow rate. Flow of organosiliconvapor is controlled by the organosilicon shut-off valve 592. Pressure isapplied to the headspace 614 of the liquid reservoir 588, for example apressure in the range of 0-15 psi (0 to 78 cm·Hg), from a pressuresource 616 such as pressurized air connected to the headspace 614 by apressure line 618 to establish repeatable organosilicon liquid deliverythat is not dependent on atmospheric pressure (and the fluctuationstherein). The reservoir 588 is sealed and the capillary connection 620is at the bottom of the reservoir 588 to ensure that only neatorganosilicon liquid (not the pressurized gas from the headspace 614)flows through the capillary tube 590. The organosilicon liquidoptionally can be heated above ambient temperature, if necessary ordesirable to cause the organosilicon liquid to evaporate, forming anorganosilicon vapor. Oxygen is provided from the oxygen tank 594 via anoxygen feed line 596 controlled by a mass flow controller 598 andprovided with an oxygen shut-off valve 600.

IV.A. In the embodiment of FIG. 7, the station or device 26 can includea vacuum source 98 adapted for seating on the vacuum port 96, a sidechannel 134 connected to the probe 108, or both (as illustrated). In theillustrated embodiment, the side channel 134 includes a shut-off valve136 that regulates flow between a probe port 138 and a vacuum port 140.In the illustrated embodiment, the selection valve 136 has at least twostates: an evacuation state in which the ports 138 and 140 areconnected, providing two parallel paths for gas flow (thus increasingthe rate of pumping or decreasing the pumping effort) and adisconnection state in which the ports 138 and 140 are isolated.Optionally, the selection valve 136 can have a third port, such as aPECVD gas inlet port 142, for introducing PECVD reactive and processgases from a gas source 144. This expedient allows the same vacuumsupply and probe 108 to be used both for leak or permeation testing andfor applying the barrier or other type of coating.

IV.A. In the illustrated embodiments, the vacuum line such as 146 to thevacuum source 98 can also include a shut-off valve 148. The shut-offvalves 136 and 148 can be closed when the probe 108 and vacuum source 98are not connected to a vessel holder such as 44 so the side channel 134and the vacuum line 146 do not need to be evacuated on the side of thevalves 136 and 148 away from the vessel 80 when moved from one vesselholder 44 to another. To facilitate removing the probe 108 axially fromthe gas inlet port 104, a flexible line 150 can be provided to allowaxial movement of the probe 108 independent of the position of thevacuum line 146 relative to the port 96.

IV.A. FIG. 7 also shows another optional feature usable with anyembodiment—a vent 404 to ambient air controlled by a valve 406. Thevalve 406 can be opened to break the vacuum quickly after processing thevessel 80, whether to release the vessel 80 from the vessel holder 44,to release the vessel holder 44 at the vacuum port 96 from the source ofvacuum 98, or optionally both.

IV.A. In the illustrated embodiment (still referring to FIG. 7), theprobe 108 can also be connected to a pressure gauge 152 and cancommunicate with the interior 154 of the vessel 80, allowing thepressure within the vessel 80 to be measured.

IV.A. In the apparatus of FIG. 1, the vessel coating station 28 can be,for example, a PECVD apparatus as further described below, operatedunder suitable conditions to deposit a SiO_(x) barrier or other type ofcoating 90 on the interior surface 88 of a vessel 80, as shown in FIG.2.

IV.A. Referring especially to FIGS. 1 and 2, the processing station 28can include an electrode 160 fed by a radio frequency power supply 162for providing an electric field for generating plasma within the vessel80 during processing. In this embodiment, the probe 108 is alsoelectrically conductive and is grounded, thus providing acounter-electrode within the vessel 80. Alternatively, in any embodimentthe outer electrode 160 can be grounded and the probe 108 directlyconnected to the power supply 162.

IV.A. In the embodiment of FIG. 2, the outer electrode 160 can either begenerally cylindrical as illustrated in FIGS. 2 and 8 or a generallyU-shaped elongated channel as illustrated in FIGS. 2 and 9 (FIGS. 8 and9 being alternative embodiments of the section taken along section lineA-A of FIG. 2). Each illustrated embodiment has one or more sidewalls,such as 164 and 166, and optionally a top end 168, disposed about thevessel 80 in close proximity.

IV.A., IV.B. FIGS. 12 to 19 show other variants of the vessel coatingstation or device 28 as previously described. Any one or more of thesevariants can be substituted for the vessel coating station or device 28shown in FIG. 1-5.

IV.A. FIG. 12 shows an alternative electrode system that can be used (inthe same manner as discussed above using the same vessel holder and gasinlet) at frequencies above 1 GHz. At these frequencies the electricalenergy from the power supply can be transferred to the interior of thetube through one or more waveguides that are connected to a cavity thateither absorbs the energy or resonates the energy. Resonating the energyallows it to couple to the gas. Different cavities can be provided foruse with different frequencies and vessels such as 80, since the vessel80 will interact with the cavity altering its resonation point, creatingplasma for coating and/or treatment.

IV.A. FIG. 12 shows that the coating station 28 can include a microwavepower supply 190 directing microwaves via a waveguide 192 to a microwavecavity 194 at least partially surrounding the vessel 80 within whichplasma can be to be generated. The microwave cavity 194 can be tuned, inrelation to the frequency of the microwaves and the partial pressuresand selection of gases, to absorb microwaves and couple to theplasma-generating gas. In FIG. 13, as well as any of the illustratedembodiments a small gap 196 can be left between the vessel 80 and thecavity 194 (or electrode, detector, or other surrounding structure) toavoid scratching or otherwise damaging the vessel 80. Also in FIG. 13,the microwave cavity 194 has a flat end wall 198, so the gap 196 is notuniform in width, for example opposite the circular edge of the end wall198. Optionally, the end 198 can be curved to provide a substantiallyuniform gap 196. IV.A. FIG. 44 is a view similar to FIG. 2 of analternative gas delivery tube/inner electrode 470 usable, for examplewith the embodiments of FIGS. 1, 2, 3, 8, 9, 12-16, 18-19, 21-22, 33,37-43, 46-49, and 52-54. As shown in FIG. 44, the distal portion 472 ofthe inner electrode 470 comprises an elongated porous side wall 474enclosing an internal passage 476 within the inner electrode. Theinternal passage 476 is connected to the gas feed 144 by the proximalportion 478 of the inner electrode 470 extending outside the vessel 80.The distal end 480 of the inner electrode 470 can also optionally beporous. The porosity of the porous side wall 474 and, if present, theporous distal end 480 allow at least a portion of the reactant gas fedfrom the gas feed 144 to escape laterally from the passage 476 to supplyreactant gas to the adjacent portion of the interior surface 88 of thevessel 80. In this embodiment, the porous portion of the porous sidewall 474 extends the entire length of the inner electrode 470 within thevessel 80, although the porous portion could be less extensive, runningonly a portion of the length of the inner electrode 470. As indicatedelsewhere in this specification, the inner electrode 470 could also belonger or shorter, relative to the length of the vessel 80, than isshown in FIG. 44, and the porous portion can be continuous ordiscontinuous.

IV.A. The outer diameter of the inner electrode 470 can be at least 50%as great, or at least 60% as great, or at least 70% as great, or atleast 80% as great, or at least 90% as great, or at least 95% as greatas the laterally adjacent inner diameter of the vessel. Employing alarger-diameter inner electrode 470, in relation to the inner diameterof the vessel 80, for example if the electrode 470 is concentric withthe vessel 80, reduces the distance between the exterior of the innerelectrode 470 and the adjacent interior surface 88 of the vessel 80,confining the plasma to a smaller region within which it can be moreuniform. Employing a larger-diameter inner electrode 470 also providesmore uniform distribution of the reactant gas and/or carrier gas alongthe interior surface 80, as fresh gases are introduced to the plasma atclosely spaced points along the length of the interior surface 88, veryclose to the site of initial reaction, as opposed to flowing from asingle point relative to the interior surface 88 to form.

IV.A. In one contemplated arrangement, shown in full lines, the powersupply 162 has one power connection to the electrode 200, which can beat any point along the electrode 200, and the probe 108 can be grounded.In this configuration a capacitive load can be used to generate theplasma within the vessel 80. In another contemplated arrangement, shownin phantom lines (and eliminating the connections shown in full lines),the respective leads of the power supply 162 are connected to therespective ends of the coil 200, which for convenience can be againreferred to as an “electrode” in this specification. In thisconfiguration, an inductive load can be used to generate the plasmawithin the vessel 80. A combination of inductive and capacitive loadscan also be used, in an alternative embodiment.

IV.A. FIGS. 46-48 show an array of two or more gas delivery tubes suchas 108 (also shown in FIG. 2), 510, and 512, which are also innerelectrodes. The array can be linear or a carousel. A carousel arrayallows the electrodes to be reused periodically.

IV.A. FIGS. 46-48 also show an inner electrode extender and retractor514 for inserting and removing the gas delivery tubes/inner electrodes108, 510, and 512 into and from one or more vessel holders such as 50 or48. These features are optional expedients for using the gas deliverytubes.

IV.A. In the illustrated embodiment, referring to FIGS. 46-48 as well as53, the inner electrodes 108, 510, and 512 are respectively connected byflexible hoses 516, 518, and 520 to a common gas supply 144, viashut-off valves 522, 524, and 526. (The flexible hoses are foreshortenedin FIGS. 46-48 by omitting the slack portions). Referring briefly toFIG. 56, the flexible hoses 516, 518, and 520 alternatively can beconnected to independent gas sources 144. A mechanism 514 is provided toextend and retract an inner electrode such as 108. The inner electrodeextender and retractor is configured for moving an inner electrode amonga fully advanced position, an intermediate position, and a retractedposition with respect to the vessel holder.

IV.A. In FIGS. 46 and 56, the inner electrode 108 is extended to itsoperative position within the vessel holder 50 and vessel 80, and itsshut-off valve 522 is open. Also in FIG. 46, the idle inner electrodes510 and 512 are retracted and their shut-off valves 524 and 526 areclosed. In the illustrated embodiment, one or more of the idle innerelectrodes 510 and 512 are disposed within an electrode cleaning deviceor station 528. One or more electrodes can be cleaned and othersreplaced within the station 528, optionally. The cleaning operations caninvolve chemical reaction or solvent treatment to remove deposits,milling to physically remove deposits, or plasma treatment toessentially burn away accumulated deposits, as non-limiting examples.

IV.A. In FIG. 47, the idle inner electrodes 510 and 512 are as before,while the working inner electrode 108 has been retracted out of thevessel 80, with its distal end remaining within the vessel holder 50,and its valve 522 has been closed. In this condition, the vessel 80 canbe removed and a new vessel seated on the vessel holder 50 without anydanger of touching the electrode 108 with the vessels 80 being removedand replaced. After the vessel 80 is replaced, the inner electrode 108can be advanced to the position of FIGS. 46 AND 56 and the shut-offvalve 522 can be reopened to commence coating the new vessel 80 usingthe same inner electrode 108 as before. Thus, in an arrangement in whicha series of the vessels 80 are seated on and removed from the vesselholder 50, the inner electrode 108 can be extended and partiallyretracted numerous times, as the vessel 80 is installed or removed fromthe vessel holder 50 at the station where the inner electrode 108 is inuse

IV.A. In FIG. 48, the vessel holder 50 and its vessel 80 have beenreplaced with a new vessel holder 48 and another vessel 80. Referring toFIG. 1, in this type of embodiment each vessel 80 remains on its vesselholder such as 50 or 48 and an inner electrode such as 108 is insertedinto each vessel as its vessel holder reaches the coating station.

IV.A. Additionally in FIG. 48, the inner electrodes 108, 510, and 512are fully retracted, and the array of inner electrodes 108, 510, and 512has been moved to the right relative to the vessel holder 48 andelectrode cleaning station 528, compared to the positions of each inFIG. 47, so the inner electrode 108 has been moved out of position andthe inner electrode 510 has been moved into position with respect to thevessel holder 48.

IV.A. It should be understood that the movement of the array of innerelectrodes can be independent of the movement of the vessel holders.They can be moved together or independently, to simultaneously orindependently switch to a new vessel holder and/or a new innerelectrode.

IV.A. FIGS. 46-48 show an array of two or more gas delivery tubes suchas 108 (also shown in FIG. 2), 510, and 512, which are also innerelectrodes. The array can be linear or a carousel. A carousel arrayallows the electrodes to be reused periodically.

IV.A. FIGS. 46-48 also show an inner electrode extender and retractor514 for inserting and removing the gas delivery tubes/inner electrodes108, 510, and 512 into and from one or more vessel holders such as 50 or48. These features are optional expedients for using the gas deliverytubes.

IV.A. In the illustrated embodiment, referring to FIGS. 46-48 as well as53, the inner electrodes 108, 510, and 512 are respectively connected byflexible hoses 516, 518, and 520 to a common gas supply 144, viashut-off valves 522, 524, and 526. (The flexible hoses are foreshortenedin FIGS. 46-48 by omitting the slack portions). A mechanism 514 isprovided to extend and retract an inner electrode such as 108. The innerelectrode extender and retractor is configured for moving an innerelectrode among a fully advanced position, an intermediate position, anda retracted position with respect to the vessel holder.

IV.A. In FIGS. 46 AND 56, the inner electrode 108 is extended to itsoperative position within the vessel holder 50 and vessel 80, and itsshut-off valve 522 is open. Also in FIGS. 46 AND 56, the idle innerelectrodes 510 and 512 are retracted and their shut-off valves 524 and526 are closed. In the illustrated embodiment, the idle inner electrodes510 and 512 are disposed within an electrode cleaning or station 528.Some electrodes can be cleaned and others replaced within the station528, optionally. The cleaning operations can involve chemical reactionor solvent treatment to remove deposits, milling to physically removedeposits, or plasma treatment to essentially burn away accumulateddeposits, as non-limiting examples.

IV.A. In FIG. 47, the idle inner electrodes 510 and 512 are as before,while the working inner electrode 108 has been retracted out of thevessel 80, with its distal end remaining within the vessel holder 50,and its valve 522 has been closed. In this condition, the vessel 80 canbe removed and a new vessel seated on the vessel holder 50 without anydanger of touching the electrode 108 with the vessels 80 being removedand replaced. After the vessel 80 is replaced, the inner electrode 108can be advanced to the position of FIGS. 46 AND 56 and the shut-offvalve 522 can be reopened to commence coating the new vessel 80 usingthe same inner electrode 108 as before. Thus, in an arrangement in whicha series of the vessels 80 are seated on and removed from the vesselholder 50, the inner electrode 108 can be extended and partiallyretracted numerous times, as the vessel 80 is installed or removed fromthe vessel holder 50 at the station where the inner electrode 108 is inuse

IV.A. In FIG. 48, the vessel holder 50 and its vessel 80 have beenreplaced with a new vessel holder 48 and another vessel 80. Referring toFIG. 1, in this type of embodiment each vessel 80 remains on its vesselholder such as 50 or 48 and an inner electrode such as 108 is insertedinto each vessel as its vessel holder reaches the coating station.

IV.A. Additionally in FIG. 48, the inner electrodes 108, 510, and 512are fully retracted, and the array of inner electrodes 108, 510, and 512has been moved to the right relative to the vessel holder 48 andelectrode cleaning station 528, compared to the positions of each inFIG. 47, so the inner electrode 108 has been moved out of position andthe inner electrode 510 has been moved into position with respect to thevessel holder 48.

IV.A. It should be understood that the movement of the array of innerelectrodes can be independent of the movement of the vessel holders.They can be moved together or independently, to simultaneously orindependently switch to a new vessel holder and/or a new innerelectrode.

IV.A. An array of two or more inner electrodes 108, 510, and 512 isuseful because the individual combined gas delivery tubes/innerelectrodes 108, 510, and 512 will in some instances tend to accumulatepolymerized reactant gases or some other type of deposits as they areused to coat a series of vessels such as 80. The deposits can accumulateto the point at which they detract from the coating rate or uniformityproduced, which can be undesirable. To maintain a uniform process, theinner electrodes can be periodically removed from service, replaced orcleaned, and a new or cleaned electrode can be put into service. Forexample, going from FIG. 46 to FIG. 48, the inner electrode 108 has beenreplaced with a fresh or reconditioned inner electrode 510, which isready to be extended into the vessel holder 48 and the vessel 80 toapply an interior coating to the new vessel.

IV.A. Thus, an inner electrode drive 530 is operable in conjunction withthe inner electrode extender and retractor 514 for removing a firstinner electrode 108 from its extended position to its retractedposition, substituting a second inner electrode 510 for the first innerelectrode 108, and advancing the second inner electrode 510 to itsextended position (analogous to FIGS. 46 and 56 except for thesubstitution of electrode).

IV.A. The array of gas delivery tubes of FIGS. 46-48 and inner electrodedrive 530 are usable, for example, with the embodiments of FIGS. 1, 2,3, 8, 9, 12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49, and 52-54. Theextending and retracting mechanism 514 of FIGS. 46-48 is usable, forexample, with the gas delivery tube embodiments of FIGS. 2, 3, 8, 9,12-16, 18-19, 21-22, 26-28, 33-35, 37-45, 49, and 52-54, as well as withthe probes of the vessel inspection apparatus of FIGS. 6 and 7.

IV.A The electrode 160 shown in FIG. 2 can be shaped like a “U” channelwith its length into the page and the puck or vessel holder 50 can movethrough the activated (powered) electrode during the treatment/coatingprocess. Note that since external and internal electrodes are used, thisapparatus can employ a frequency between 50 Hz and 1 GHz applied from apower supply 162 to the U channel electrode 160. The probe 108 can begrounded to complete the electrical circuit, allowing current to flowthrough the low-pressure gas(es) inside of the vessel 80. The currentcreates plasma to allow the selective treatment and/or coating of theinterior surface 88 of the device.

IV.A The electrode in FIG. 2 can also be powered by a pulsed powersupply. Pulsing allows for depletion of reactive gases and then removalof by-products prior to activation and depletion (again) of the reactivegases. Pulsed power systems are typically characterized by their dutycycle which determines the amount of time that the electric field (andtherefore the plasma) is present. The power-on time is relative to thepower-off time. For example a duty cycle of 10% can correspond to apower on time of 10% of a cycle where the power was off for 90% of thetime. As a specific example, the power might be on for 0.1 second andoff for 1 second. Pulsed power systems reduce the effective power inputfor a given power supply 162, since the off-time results in increasedprocessing time. When the system is pulsed, the resulting coating can bevery pure (no by products or contaminants). Another result of pulsedsystems is the possibility to achieve atomic layer deposition (ALD). Inthis case, the duty cycle can be adjusted so that the power-on timeresults in the deposition of a single layer of a desired material. Inthis manner, a single atomic layer is contemplated to be deposited ineach cycle. This approach can result in highly pure and highlystructured coatings (although at the temperatures required fordeposition on polymeric surfaces, temperatures optionally are kept low(<100.degree. C.) and the low-temperature coatings can be amorphous).

IV.A. An alternative coating station is disclosed in FIG. 12, employinga microwave cavity instead of an outer electrode. The energy applied canbe a microwave frequency, for example 2.45 GHz.

IV.B. PECVD Apparatus Using Gripper for Transporting Tube to and fromCoating Station

IV.B. Another embodiment is an apparatus for PECVD treatment of avessel, employing a gripper as previously described. FIGS. 15 and 16show apparatus generally indicated at 202 for PECVD treatment of a firstvessel 80 having an open end 82, a closed end 84, and an interior spacedefined by the surface 88. This embodiment includes a vessel holder 48,at least a first gripper 204 (in this embodiment, for example, a suctioncup), a seat defined by the vessel port 92 on the vessel holder 48, areactant supply 144, a plasma generator represented by the electrodes108 and 160, a vessel release, which can be a vent valve such as 534,and either the same gripper 204 or a second one (in effect, optionally asecond gripper 204).

IV.B. The first gripper 204, and as illustrated any of the grippers 204,is configured for selectively holding and releasing the closed end 84 ofa vessel 80. While gripping the closed end 84 of the vessel, the firstgripper 204 can transport the vessel to the vicinity of the vesselholder 48. In the illustrated embodiment, the transportation function isfacilitated by a series conveyor 538 to which the grippers 204 areattached in a series.

IV.B. The vessel holder 48 has previously been described in connectionwith other embodiments, and is configured for seating to the open end 82of a vessel 80. The seat defined by the vessel port 92 has previouslybeen described in connection with other embodiments, and is configuredfor establishing sealed communication between the vessel holder 48 andthe interior space 88 of the first vessel, and in this case any of thevessels 80. The reactant supply 144 has previously been described inconnection with other embodiments, and is operatively connected forintroducing at least one gaseous reactant within the first vessel 80through the vessel holder 48. The plasma generator defined by theelectrodes 108 and 160 has previously been described in connection withother embodiments, and is configured for forming plasma within the firstvessel under conditions effective to form a reaction product of thereactant on the interior surface of the first vessel.

IV.B. The vessel release 534 or other expedients, such as introducingwithin the seated vessel 80 a reactant gas, a carrier gas, or aninexpensive gas such as compressed nitrogen or air, can be used forunseating the first vessel 80 from the vessel holder 48.

IV.B. The grippers 204 are configured for axially transporting the firstvessel 80 away from the vessel holder 48 and then releasing the firstvessel 80, as by releasing suction from between the gripper 48 and thevessel end 84.

IV.B. FIGS. 15 and 16 also show a method of PECVD treatment of a firstvessel, comprising several steps. A first vessel 80 is provided havingan open end 82, a closed end 84, and an interior surface 88. At least afirst gripper 204 is provided that is configured for selectively holdingand releasing the closed end 84 of the first vessel 80. The closed end84 of the first vessel 80 is gripped with the first gripper 204 andthereby transported to the vicinity of a vessel holder 48 configured forseating to the open end of the first vessel. In the embodiment of FIG.16, two vessel holders 48 are provided, allowing the vessels 80 to beadvanced and seated on the vessel holders 48 two at a time, thusdoubling the effective production rate. Next, the first gripper 204 isused for axially advancing the first vessel 80 and seating its open end82 on the vessel holder 48, establishing sealed communication betweenthe vessel holder 48 and the interior of the first vessel. Next, atleast one gaseous reactant is introduced within the first vessel throughthe vessel holder, optionally as explained for previous embodiments.

IV.B. Continuing, plasma is formed within the first vessel underconditions effective to form a reaction product of the reactant on theinterior surface of the first vessel, optionally as explained forprevious embodiments. The first vessel is unseated from the vesselholder, optionally as explained for previous embodiments. The firstgripper or another gripper is used, optionally as explained for previousembodiments, to axially transport the first vessel away from the vesselholder. The first vessel can then be released from the gripper used toaxially transport it away from the vessel holder, optionally asexplained for previous embodiments.

IV.B. Further optional steps that can be carried out according to thismethod include providing a reaction vessel different from the firstvessel, the reaction vessel having an open end and an interior space,and seating the open end of the reaction vessel on the vessel holder,establishing sealed communication between the vessel holder and theinterior space of the reaction vessel. A PECVD reactant conduit can beprovided within the interior space. Plasma can be formed within theinterior space of the reaction vessel under conditions effective toremove at least a portion of a deposit of a PECVD reaction product fromthe reactant conduit. These reaction conditions have been explained inconnection with a previously described embodiment. The reaction vesselthen can be unseated from the vessel holder and transported away fromthe vessel holder.

IV.B. Further optional steps that can be carried out according to anyembodiment of this method include:

-   -   providing at least a second gripper;    -   operatively connecting at least the first and second grippers to        a series conveyor;    -   providing a second vessel having an open end, a closed end, and        an interior surface;    -   providing a gripper configured for selectively holding and        releasing the closed end of the second vessel;    -   gripping the closed end of the second vessel with the gripper;    -   using the gripper, transporting the second vessel to the        vicinity of a vessel holder configured for seating to the open        end of the second vessel;    -   using the gripper, axially advancing the second vessel and        seating its open end on the vessel holder, establishing sealed        communication between the vessel holder and the interior of the        second vessel;    -   introducing at least one gaseous reactant within the second        vessel through the vessel holder;    -   forming plasma within the second vessel under conditions        effective to form a reaction product of the reactant on the        interior surface of the second vessel;    -   unseating the second vessel from the vessel holder; and    -   using the second gripper or another gripper, axially        transporting the second vessel away from the vessel holder; and    -   releasing the second vessel from the gripper used to axially        transport it away from the vessel holder.

IV.B. FIG. 16 is an example of using a suction cup type device to holdthe end of a sample collection tube (in this example) that can movethrough a production line/system. The specific example shown here is onepossible step (of many possible steps as outlined above and below) ofcoating/treatment. The tube can move into the coating step/area and thetube can be lowered into the vessel holder and (in this example) thecylindrical electrode. The vessel holder, sample collection tube andsuction cup can then move together to the next step where the electrodeis powered and the treatment/coating take place. Any of the above typesof electrodes can be utilized in this example.

IV.B. Thus, FIGS. 15 and 16 show a vessel holder 48 in a coating station28 similar to FIG. 13, employing a vessel transport generally indicatedas 202 to move the vessel 80 to and from the coating station 28. Thevessel transport 202 can be provided with a grip 204, which in theillustrated transport 202 can be a suction cup. An adhesive pad, activevacuum source (with a pump to draw air from the grip, actively creatinga vacuum) or other expedient can also be employed as the grip. Thevessel transport 202 can be used, for example, to lower the vessel 80into a seated position in the vessel port 92 to position the vessel 80for coating. The vessel transport 202 can also be used to lift thevessel 80 away from the vessel port 92 after processing at the station28 can be complete. The vessel transport 202 also can be used to seatthe vessel 80 before the vessel 80 and vessel transport 48 are advancedtogether to a station. The vessel transport can also be used to urge thevessel 80 against its seat on the vessel port 92. Also, although FIG. 15can be oriented to show vertical lifting of the vessel 80 from above, aninverted orientation can be or contemplated in which the vesseltransport 202 is below the vessel 80 and supports it from beneath.

IV.B. FIG. 16 shows an embodiment of a method in which vessel transports202 such as suction cups 204 convey the vessels 80 horizontally, as fromone station to the next, as well as (or instead of) vertically into andout of a station such as 28. The vessels 80 can be lifted andtransported in any orientation. FIG. 16 thus represents a method ofPECVD treatment of a first vessel 80, comprising several steps.

IV.B. In the embodiment of FIG. 13, the outer electrode 160 can begenerally cylindrical with open ends, and can be stationary. The vessel80 can be advanced through the outer electrode 160 until the opening 82is seated on the vessel port 96. In this embodiment, the probe 108optionally can be permanently molded or otherwise secured into the gasinlet port 104, as opposed to a wiping seal allowing relative motionbetween the port 104 and the probe 108.

IV.B. FIG. 14 shows an additional alternative for coupling electricalenergy into the plasma at 50 Hz-1 GHz. This can consist of a coil thatcan be either lowered into position or the vessel holder (with device)can be pushed up into position. Coiled electrodes are referred to asinductive coupling devices and can impart a magnetic component to theinside of the device where the plasma can be created.

IV.B. A probe 108 can still be used as discussed in FIG. 2 and FIG. 13.Other aspects of the vessel holder or vessel holder 48 discussed abovecan remain the same.

IV.B. As FIG. 49 for example shows, a reaction vessel 532 different fromthe first vessel 80 can be provided, also having an open end 540 and aninterior space defined by the interior surface 542. Like the vessels 80,the reaction vessel 532 can have its open end 540 on the vessel holder48 and establish sealed communication between the vessel holder 48 andthe interior space 542 of the reaction vessel.

IV.B. FIG. 49 is a view similar to FIG. 16 showing a mechanism fordelivering vessels 80 to be treated and a cleaning reactor 532 to aPECVD coating apparatus. In this embodiment, the inner electrode 108optionally can be cleaned without removing it from the vessel holder 48.

IV.B. FIG. 49 shows that the PECVD reactant conduit 108 as previouslydescribed is positioned to be located within the interior space 542 ofthe reaction vessel 532 when the reaction vessel is seated on the vesselholder 48 in place of a vessel 80 which is provided for coating asdescribed previously. FIG. 49 shows the reactant conduit 108 in thisconfiguration, even though the conduit 108 has an exterior portion, aswell as an interior distal end. It suffices for this purpose and thepresent claims if the reactant conduit 108 extends at least partiallyinto the vessel 80 or 532.

IV.B. The mechanism of FIG. 49 as illustrated is usable with theembodiments of at least FIGS. 1 and 15-16, for example. The cleaningreactor 532 can also be provided as a simple vessel seated andtransported on a vessel holder such as 48, in an alternative embodiment.In this configuration, the cleaning reactor 532 can be used with theapparatus of at least FIGS. 1-3, 8, 9, 12-15, 18, 19, 21, 22, 26-28,33-35, 37-48, and 52-54, for example.

IV.B. The plasma generator defined by the electrodes 108 and 160 isconfigurable for forming plasma within the interior space of thereaction vessel 532 under conditions effective to remove at least aportion of a deposit of a PECVD reaction product from the reactantconduit 108. It is contemplated above that the inner electrode and gassource 108 can be a conductive tube, for example a metallic tube, andthat the reaction vessel 532 can be made of any suitable, optionallyheat-resistant material such as ceramic, quartz, glass or othermaterials that can withstand more heat than a thermoplastic vessel. Thematerial of the reaction vessel 532 also can desirably be chemical orplasma resistant to the conditions used in the reaction vessel to removedeposits of reaction products. Optionally, the reaction vessel 532 canbe made of electrically conductive material and itself serve as aspecial-purpose outer electrode for the purpose of removing depositsfrom the reactant conduit 108. As yet another alternative, the reactionvessel 532 can be configured as a cap that seats on the outer electrode160, in which case the outer electrode 160 would optionally be seated onthe vessel holder 48 to define a closed cleaning reaction chamber.

IV.B. It is contemplated that the reaction conditions effective toremove at least a portion of a deposit of a PECVD reaction product fromthe reactant conduit 108 include introduction of a substantial portionof an oxidizing reactant such as oxygen or ozone (either generatedseparately or by the plasma apparatus), a higher power level than isused for deposition of coatings, a longer cycle time than is used fordeposition of coatings, or other expedients known for removing the typeof unwanted deposit encountered on the reaction conduit 108. For anotherexample, mechanical milling can also be used to remove unwanteddeposits. Or, solvents or other agents can be forced through thereactant conduit 108 to clear obstructions. These conditions can be farmore severe than what the vessels 80 to be coated can withstand, sincethe reaction vessel 532 does not need to be suitable for the normal usesof the vessel 80. Optionally, however, a vessel 80 can be used as thereaction vessel, and if the deposit removing conditions are too severethe vessel 80 employed as a reaction vessel can be discarded, in analternative embodiment.

V. PECVD Methods for Making Vessels

V.1 Precursors for PECVD Coating

The precursor for the PECVD coating of the present invention is broadlydefined as an organometallic precursor. An organometallic precursor isdefined in this specification as comprehending compounds of metalelements from Group III and/or Group IV of the Periodic Table havingorganic residues, e.g. hydrocarbon, aminocarbon or oxycarbon residues.Organometallic compounds as presently defined include any precursorhaving organic moieties bonded to silicon or other Group III/IV metalatoms directly, or optionally bonded through oxygen or nitrogen atoms.The relevant elements of Group III of the Periodic Table are Boron,Aluminum, Gallium, Indium, Thallium, Scandium, Yttrium, and Lanthanum,Aluminum and Boron being preferred. The relevant elements of Group IV ofthe Periodic Table are Silicon, Germanium, Tin, Lead, Titanium,Zirconium, Hafnium, and Thorium, with Silicon and Tin being preferred.Other volatile organic compounds can also be contemplated. However,organosilicon compounds are preferred for performing present invention.

An organosilicon precursor is contemplated, where an “organosiliconprecursor” is defined throughout this specification most broadly as acompound having at least one of the linkages:

The first structure immediately above is a tetravalent silicon atomconnected to an oxygen atom and an organic carbon atom (an organiccarbon atom being a carbon atom bonded to at least one hydrogen atom).The second structure immediately above is a tetravalent silicon atomconnected to an —NH— linkage and an organic carbon atom (an organiccarbon atom being a carbon atom bonded to at least one hydrogen atom).Optionally, the organosilicon precursor is selected from the groupconsisting of a linear siloxane, a monocyclic siloxane, a polycyclicsiloxane, a polysilsesquioxane, a linear silazane, a monocyclicsilazane, a polycyclic silazane, a polysilsesquiazane, and a combinationof any two or more of these precursors. Also contemplated as aprecursor, though not within the two formulas immediately above, is analkyl trimethoxysilane.

If an oxygen-containing precursor (e.g. a siloxane) is used, arepresentative predicted empirical composition resulting from PECVDunder conditions forming a hydrophobic or lubricating coating would beSi_(w)O_(x)C_(y)H_(z) as defined in the Definition Section, while arepresentative predicted empirical composition resulting from PECVDunder conditions forming a barrier layer would be SiO_(x), where x inthis formula is from about 1.5 to about 2.9. If a nitrogen-containingprecursor (e.g. a silazane) is used, the predicted composition would beSi.sub.w*N.sub.x*C.sub.y*H.sub.z*Si_(w)*N_(x)*C_(y)*H_(z)*, i.e. inSi_(w)O_(x)C_(y)H_(z) as specified in the Definition Section, O isreplaced by N and the indices are adapted to the higher valency of N ascompared to O (3 instead of 2). The latter adaptation will generallyfollow the ratio of w, x, y and z in a siloxane to the correspondingindices in its aza counterpart. In a particular aspect of the invention,Si_(w)*N_(x)*C_(y)*H_(z)* in which w*, x*, y*, and z* are defined thesame as w, x, y, and z for the siloxane counterparts, but for anoptional deviation in the number of hydrogen atoms.

One type of precursor starting material having the above empiricalformula is a linear siloxane, for example a material having thefollowing formula:

in which each R is independently selected from alkyl, for examplemethyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl,alkyne, or others, and n is 1, 2, 3, 4, or greater, optionally two orgreater. Several examples of contemplated linear siloxanes are [0263]hexamethyldisiloxane (HMDSO), [0264] octamethyltrisiloxane, [0265]decamethyltetrasiloxane, [0266] dodecamethylpentasiloxane, orcombinations of two or more of these. The analogous silazanes in which—NH— is substituted for the oxygen atom in the above structure are alsouseful for making analogous coatings. Several examples of contemplatedlinear silazanes are octamethyltrisilazane, decamethyltetrasilazane, orcombinations of two or more of these.

V.C. Another type of precursor starting material is a monocyclicsiloxane, for example a material having the following structuralformula:

in which R is defined as for the linear structure and “a” is from 3 toabout 10, or the analogous monocyclic silazanes. Several examples ofcontemplated hetero-substituted and unsubstituted monocyclic siloxanesand silazanes include

-   1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)methyl]cyclotrisiloxane-   2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane,-   pentamethylcyclopentasiloxane,-   pentavinylpentamethylcyclopentasiloxane,-   hexamethylcyclotrisiloxane,-   hexaphenylcyclotrisiloxane,-   octamethylcyclotetrasiloxane (OMCTS),-   octaphenylcyclotetrasiloxane,-   decamethylcyclopentasiloxane-   dodecamethylcyclohexasiloxane,-   methyl(3,3,3-trifluoropropl)cyclosiloxane,-   Cyclic organosilazanes are also contemplated, such as-   Octamethylcyclotetrasilazane,-   1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane    hexamethylcyclotrisilazane,-   octamethylcyclotetrasilazane,-   decamethylcyclopentasilazane,-   dodecamethylcyclohexasilazane, or combinations of any two or more of    these.

V.C. Another type of precursor starting material is a polycyclicsiloxane, for example a material having one of the following structuralformulas:

in which Y can be oxygen or nitrogen, E is silicon, and Z is a hydrogenatom or an organic substituent, for example alkyl such as methyl, ethyl,propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl, alkyne, or others.When each Y is oxygen, the respective structures, from left to right,are a silatrane, a silquasilatrane, and a silproatrane. When Y isnitrogen, the respective structures are an azasilatrane, anazasilquasiatrane, and an azasilproatrane.

V.C. Another type of polycyclic siloxane precursor starting material isa polysilsesquioxane, with the empirical formula RSiO_(1.5) and thestructural formula shown as a T₈ cube:

in which each R is a hydrogen atom or an organic substituent, forexample alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,t-butyl, vinyl, alkyne, or others. Two commercial materials of this sortare a T₈ cube, available as a commercial product SST-eM01poly(methylsilsesquioxane), in which each R is methyl, and another T₈cube, available as a commercial product SST-3 MH1.1poly(Methyl-Hydridosilsesquioxane), in which 90% of the R groups aremethyl, 10% are hydrogen atoms. This material is available in a 10%solution in tetrahydrofuran, for example. Combinations of two or more ofthese are also contemplated. Other examples of a contemplated precursorare methylsilatrane, CAS No. 2288-13-3, in which each Y is oxygen and Zis methyl, methylazasilatrane, or a combination of any two or more ofthese.

V.C. The analogous polysilsesquiazanes in which —NH— is substituted forthe oxygen atom in the above structure are also useful for makinganalogous coatings. Examples of contemplated polysilsesquiazanes are apoly(methylsilsesquiazane), in which each R is methyl, and apoly(Methyl-Hydridosilsesquiazane, in which 90% of the R groups aremethyl, 10% are hydrogen atoms. Combinations of two or more of these arealso contemplated.

V.C. One particularly contemplated precursor for the lubricity layeraccording to the present invention is a monocyclic siloxane, for exampleis octamethylcyclotetrasiloxane.

One particularly contemplated precursor for the hydrophobic layeraccording to the present invention is a monocyclic siloxane, for exampleis octamethylcyclotetrasiloxane.

One particularly contemplated precursor for the barrier layer accordingto the present invention is a linear siloxane, for example is HMDSO.

V.C. In any of the coating methods according to the present invention,the applying step optionally can be carried out by vaporizing theprecursor and providing it in the vicinity of the substrate. E.g., OMCTSis usually vaporized by heating it to about 50.degree. C. beforeapplying it to the PECVD apparatus.

V.2 General PECVD Method

In the context of the present invention, the following PECVD method isgenerally applied, which contains the following steps:

(a) providing a gaseous reactant comprising a precursor as definedherein, optionally an organosilicon precursor, and optionally O₂ in thevicinity of the substrate surface; and

(b) generating a plasma from the gaseous reactant, thus forming acoating on the substrate surface by plasma enhanced chemical vapordeposition (PECVD).

In the method, the coating characteristics are advantageously set by oneor more of the following conditions: the plasma properties, the pressureunder which the plasma is applied, the power applied to generate theplasma, the presence and relative amount of O₂ in the gaseous reactant,the plasma volume, and the organosilicon precursor. Optionally, thecoating characteristics are set by the presence and relative amount ofO₂ in the gaseous reactant and/or the power applied to generate theplasma.

In all embodiments of the present invention, the plasma is in anoptional aspect a non-hollow-cathode plasma.

In a further preferred aspect, the plasma is generated at reducedpressure (as compared to the ambient or atmospheric pressure).Optionally, the reduced pressure is less than 300 mTorr, optionally lessthan 200 mTorr, even optionally less than 100 mTorr.

The PECVD optionally is performed by energizing the gaseous reactantcontaining the precursor with electrodes powered at a frequency atmicrowave or radio frequency, and optionally at a radio frequency. Theradio frequency preferred to perform an embodiment of the invention willalso be addressed as “RF frequency”. A typical radio frequency range forperforming the present invention is a frequency of from 10 kHz to lessthan 300 MHz, optionally from 1 to 50 MHz, even optionally from 10 to 15MHz. A frequency of 13.56 MHz is most preferred, this being a governmentsanctioned frequency for conducting PECVD work.

There are several advantages for using a RF power source versus amicrowave source: Since RF operates a lower power, there is less heatingof the substrate/vessel. Because the focus of the present invention isputting a plasma coating on plastic substrates, lower processingtemperature are desired to prevent melting/distortion of the substrate.To prevent substrate overheating when using microwave PECVD, themicrowave PECVD is applied in short bursts, by pulsing the power. Thepower pulsing extends the cycle time for the coating, which is undesiredin the present invention. The higher frequency microwave can also causeoffgassing of volatile substances like residual water, oligomers andother materials in the plastic substrate. This offgassing can interferewith the PECVD coating. A major concern with using microwave for PECVDis delamination of the coating from the substrate. Delamination occursbecause the microwaves change the surface of the substrate prior todepositing the coating layer. To mitigate the possibility ofdelamination, interface coating layers have been developed for microwavePECVD to achieve good bonding between the coating and the substrate. Nosuch interface coating layer is needed with RF PECVD as there is no riskof delamination. Finally, the lubricity layer and hydrophobic layeraccording to the present invention are advantageously applied usinglower power. RF power operates at lower power and provides more controlover the PECVD process than microwave power. Nonetheless, microwavepower, though less preferred, is usable under suitable processconditions.

Furthermore, for all PECVD methods described herein, there is a specificcorrelation between the power (in Watts) used to generate the plasma andthe volume of the lumen wherein the plasma is generated. Typically, thelumen is the lumen of a vessel coated according to the presentinvention. The RF power should scale with the volume of the vessel ifthe same electrode system is employed. Once the composition of a gaseousreactant, for example the ratio of the precursor to O₂, and all otherparameters of the PECVD coating method but the power have been set, theywill typically not change when the geometry of a vessel is maintainedand only its volume is varied. In this case, the power will be directlyproportional to the volume. Thus, starting from the power to volumeratios provided by present description, the power which has to beapplied in order to achieve the same or a similar coating in a vessel ofsame geometry, but different size, can easily be found. The influence ofthe vessel geometry on the power to be applied is illustrated by theresults of the Examples for tubes in comparison to the Examples forsyringe barrels.

For any coating of the present invention, the plasma is generated withelectrodes powered with sufficient power to form a coating on thesubstrate surface. For a lubricity layer or hydrophobic layer, in themethod according to an embodiment of the invention the plasma isoptionally generated

(i) with electrodes supplied with an electric power of from 0.1 to 25 W,optionally from 1 to 22 W, optionally from 3 to 17 W, even optionallyfrom 5 to 14 W, optionally from 7 to 11 W, for example of 8 W; and/or(ii) wherein the ratio of the electrode power to the plasma volume isless than 10 W/ml, optionally is from 5 W/ml to 0.1 W/ml, optionally isfrom 4 W/ml to 0.1 W/ml, optionally from 2 W/ml to 0.2 W/ml. For abarrier layer or SiO_(x) coating, the plasma is optionally generated (i)with electrodes supplied with an electric power of from 8 to 500 W,optionally from 20 to 400 W, optionally from 35 to 350 W, evenoptionally from 44 to 300 W, optionally from 44 to 70 W; and/or

(ii) the ratio of the electrode power to the plasma volume is equal ormore than 5 W/ml, optionally is from 6 W/ml to 150 W/ml, optionally isfrom 7 W/ml to 100 W/ml, optionally from 7 W/ml to 20 W/ml.

The vessel geometry can also influence the choice of the gas inlet usedfor the PECVD coating. In a particular aspect, a syringe can be coatedwith an open tube inlet, and a tube can be coated with a gas inlethaving small holes which is extended into the tube.

The power (in Watts) used for PECVD also has an influence on the coatingproperties. Typically, an increase of the power will increase thebarrier properties of the coating, and a decrease of the power willincrease the lubricity and hydrophobicity of the coating. E.g., for acoating on the inner wall of syringe barrel having a volume of about 3ml, a power of less than 30 W will lead to a coating which ispredominantly a barrier layer, while a power of more than 30 W will leadto a coating which is predominantly a lubricity layer (see Examples).

A further parameter determining the coating properties is the ratio ofO₂ (or another oxidizing agent) to the precursor (e.g. organosiliconprecursor) in the gaseous reactant used for generating the plasma.Typically, an increase of the O₂ ratio in the gaseous reactant willincrease the barrier properties of the coating, and a decrease of the O₂ratio will increase the lubricity and hydrophobicity of the coating.

If a lubricity layer is desired, then O₂ is optionally present in avolume-volume ratio to the gaseous reactant of from 0:1 to 5:1,optionally from 0:1 to 1:1, even optionally from 0:1 to 0.5:1 or evenfrom 0:1 to 0.1:1. Most advantageously, essentially no oxygen is presentin the gaseous reactant. Thus, the gaseous reactant should comprise lessthan 1 vol % O₂, for example less than 0.5 vol % O₂, and optionally isO₂-free. The same applies to a hydrophobic layer.

If, on the other hand, a barrier or SiO_(x) coating is desired, then theO₂ is optionally present in a volume:volume ratio to the gaseousreactant of from 1:1 to 100:1 in relation to the silicon containingprecursor, optionally in a ratio of from 5:1 to 30:1, optionally in aratio of from 10:1 to 20:1, even optionally in a ratio of 15:1.

V.A. PECVD to Apply SiO_(x) Barrier Layer, Using Plasma that isSubstantially Free of Hollow Cathode Plasma

V.A. A specific embodiment is a method of applying a barrier layer ofSiO_(x), defined in this specification (unless otherwise specified in aparticular instance) as a coating containing silicon, oxygen, andoptionally other elements, in which x, the ratio of oxygen to siliconatoms, is from about 1.5 to about 2.9, or 1.5 to about 2.6, or about 2.These alternative definitions of x apply to any use of the term SiO_(x)in this specification. The barrier layer is applied to the interior of avessel, for example a sample collection tube, a syringe barrel, oranother type of vessel. The method includes several steps.

V.A. A vessel wall is provided, as is a reaction mixture comprisingplasma forming gas, i.e. an organosilicon compound gas, optionally anoxidizing gas, and optionally a hydrocarbon gas.

V.A. Plasma is formed in the reaction mixture that is substantially freeof hollow cathode plasma. The vessel wall is contacted with the reactionmixture, and the coating of SiO_(x) is deposited on at least a portionof the vessel wall.

V.A. In certain embodiments, the generation of a uniform plasmathroughout the portion of the vessel to be coated is contemplated, as ithas been found in certain instances to generate an SiO_(x) coatingproviding a better barrier against oxygen. Uniform plasma means regularplasma that does not include a substantial amount of hollow cathodeplasma (which has a higher emission intensity than regular plasma and ismanifested as a localized area of higher intensity interrupting the moreuniform intensity of the regular plasma).

V.A. The hollow cathode effect is generated by a pair of conductivesurfaces opposing each other with the same negative potential withrespect to a common anode. If the spacing is made (depending on thepressure and gas type) such that the space charge sheaths overlap,electrons start to oscillate between the reflecting potentials of theopposite wall sheaths leading to multiple collisions as the electronsare accelerated by the potential gradient across the sheath region. Theelectrons are confined in the space charge sheath overlap which resultsin very high ionization and high ion density plasmas. This phenomenon isdescribed as the hollow cathode effect. Those skilled in the art areable to vary the processing conditions, such as the power level and thefeed rates or pressure of the gases, to form uniform plasma throughoutor to form plasma including various degrees of hollow cathode plasma.

V.A. In an alternate method, using for example the apparatus of FIG. 12previously described, microwave energy can be used to generate theplasma in a PECVD process. The processing conditions can be different,however, as microwave energy applied to a thermoplastic vessel willexcite (vibrate) water molecules. Since there is a small amount of waterin all plastic materials, the microwaves will heat the plastic. As theplastic heats, the large driving force created by the vacuum inside ofthe device relative to atmospheric pressure outside the device will pullfree or easily desorb materials to the interior surface 88 where theywill either become volatile or will be weakly bound to the surface. Theweakly bound materials will then create an interface that can hindersubsequent coatings (deposited from the plasma) from adhering to theplastic interior surface 88 of the device.

V.A. As one way to negate this coating hindering effect, a coating canbe deposited at very low power (in the example above 5 to 20 Watts at2.45 GHz) creating a cap onto which subsequent coatings can adhere. Thisresults in a two-step coating process (and two coating layers). In theexample above, the initial gas flows (for the capping layer) can bechanged to 2 sccm (“standard cubic centimeters per minute”) HMDSO and 20sccm oxygen with a process power of 5 to 20 Watts for approximately 2-10seconds. Then the gases can be adjusted to the flows in the exampleabove and the power level increased to 20-50 Watts so that an SiO_(x)coating, in which x in this formula is from about 1.5 to about 2.9,alternatively from about 1.5 to about 2.6, alternatively about 2, can bedeposited. Note that the capping layer might provide little to nofunctionality in certain embodiments, except to stop materials frommigrating to the vessel interior surface 88 during the higher powerSiO_(x) coating deposition. Note also that migration of easily desorbedmaterials in the device walls typically is not an issue at lowerfrequencies such as most of the RF range, since the lower frequencies donot excite (vibrate) molecular species.

V.A. As another way to negate the coating hindering effect describedabove, the vessel 80 can be dried to remove embedded water beforeapplying microwave energy. Desiccation or drying of the vessel 80 can beaccomplished, for example, by thermally heating the vessel 80, as byusing an electric heater or forced air heating. Desiccation or drying ofthe vessel 80 also can be accomplished by exposing the interior of thevessel 80, or gas contacting the interior of the vessel 80, to adesiccant. Other expedients for drying the vessel, such as vacuumdrying, can also be used. These expedients can be carried out in one ormore of the stations or devices illustrated or by a separate station ordevice.

V.A. Additionally, the coating hindering effect described above can beaddressed by selection or processing of the resin from which the vessels80 are molded to minimize the water content of the resin.

V.B. PECVD Coating Restricted Opening of Vessel (Syringe Capillary)

V.B. FIGS. 26 and 27 show a method and apparatus generally indicated at290 for coating an inner surface 292 of a restricted opening 294 of agenerally tubular vessel 250 to be processed, for example the restrictedfront opening 294 of a syringe barrel 250, by PECVD. The previouslydescribed process is modified by connecting the restricted opening 294to a processing vessel 296 and optionally making certain othermodifications.

V.B. The generally tubular vessel 250 to be processed includes an outersurface 298, an inner or interior surface 254 defining a lumen 300, alarger opening 302 having an inner diameter, and a restricted opening294 that is defined by an inner surface 292 and has an inner diametersmaller than the inner diameter of the larger opening 302.

V.B. The processing vessel 296 has a lumen 304 and a processing vesselopening 306, which optionally is the only opening, although in otherembodiments a second opening can be provided that optionally is closedoff during processing. The processing vessel opening 306 is connectedwith the restricted opening 294 of the vessel 250 to be processed toestablish communication between the lumen 300 of the vessel 250 to beprocessed and the processing vessel lumen via the restricted opening294.

V.B. At least a partial vacuum is drawn within the lumen 300 of thevessel 250 to be processed and lumen 304 of the processing vessel 296. APECVD reactant is flowed from the gas source 144 (see FIG. 7) throughthe first opening 302, then through the lumen 300 of the vessel 250 tobe processed, then through the restricted opening 294, then into thelumen 304 of the processing vessel 296.

V.B. The PECVD reactant can be introduced through the larger opening 302of the vessel 250 by providing a generally tubular inner electrode 308having an interior passage 310, a proximal end 312, a distal end 314,and a distal opening 316, in an alternative embodiment multiple distalopenings can be provided adjacent to the distal end 314 andcommunicating with the interior passage 310. The distal end of theelectrode 308 can be placed adjacent to or into the larger opening 302of the vessel 250 to be processed. A reactant gas can be fed through thedistal opening 316 of the electrode 308 into the lumen 300 of the vessel250 to be processed. The reactant will flow through the restrictedopening 294, then into the lumen 304, to the extent the PECVD reactantis provided at a higher pressure than the vacuum initially drawn beforeintroducing the PECVD reactant.

V.B. Plasma 318 is generated adjacent to the restricted opening 294under conditions effective to deposit a coating of a PECVD reactionproduct on the inner surface 292 of the restricted opening 294. In theembodiment shown in FIG. 26, the plasma is generated by feeding RFenergy to the generally U-shaped outer electrode 160 and grounding theinner electrode 308. The feed and ground connections to the electrodescould also be reversed, though this reversal can introduce complexity ifthe vessel 250 to be processed, and thus also the inner electrode 308,are moving through the U-shaped outer electrode while the plasma isbeing generated.

V.B. The plasma 318 generated in the vessel 250 during at least aportion of processing can include hollow cathode plasma generated insidethe restricted opening 294 and/or the processing vessel lumen 304. Thegeneration of hollow cathode plasma 318 can contribute to the ability tosuccessfully apply a barrier layer at the restricted opening 294,although the invention is not limited according to the accuracy orapplicability of this theory of operation. Thus, in one contemplatedmode of operation, the processing can be carried out partially underconditions generating a uniform plasma throughout the vessel 250 and thegas inlet, and partially under conditions generating a hollow cathodeplasma, for example adjacent to the restricted opening 294.

V.B. The process is desirably operated under such conditions, asexplained here and shown in the drawings, that the plasma 318 extendssubstantially throughout the syringe lumen 300 and the restrictedopening 294. The plasma 318 also desirably extends substantiallythroughout the syringe lumen 300, the restricted opening 294, and thelumen 304 of the processing vessel 296. This assumes that a uniformcoating of the interior 254 of the vessel 250 is desired. In otherembodiments non-uniform plasma can be desired.

V.B. It is generally desirable that the plasma 318 have a substantiallyuniform color throughout the syringe lumen 300 and the restrictedopening 294 during processing, and optionally a substantially uniformcolor substantially throughout the syringe lumen 300, the restrictedopening 294, and the lumen 304 of the processing vessel 296. The plasmadesirably is substantially stable throughout the syringe lumen 300 andthe restricted opening 294, and optionally also throughout the lumen 304of the processing vessel 296.

V.B. The order of steps in this method is not contemplated to becritical.

V.B. In the embodiment of FIGS. 26 and 27, the restricted opening 294has a first fitting 332 and the processing vessel opening 306 has asecond fitting 334 adapted to seat to the first fitting 332 to establishcommunication between the lumen 304 of the processing vessel 296 and thelumen 300 of the vessel 250 to be processed.

V.B. In the embodiment of FIGS. 26 and 27, the first and second fittingsare male and female Luer lock fittings 332 and 334, respectivelyintegral with the structure defining the restricted opening 294 and theprocessing vessel opening 306. One of the fittings, in this case themale Luer lock fitting 332, comprises a locking collar 336 with athreaded inner surface and defining an axially facing, generally annularfirst abutment 338 and the other fitting 334 comprises an axiallyfacing, generally annular second abutment 340 facing the first abutment338 when the fittings 332 and 334 are engaged.

V.B. In the illustrated embodiment a seal, for example an O-ring 342 canbe positioned between the first and second fittings 332 and 334. Forexample, an annular seal can be engaged between the first and secondabutments 338 and 340. The female Luer fitting 334 also includes dogs344 that engage the threaded inner surface of the locking collar 336 tocapture the O-ring 342 between the first and second fittings 332 and334. Optionally, the communication established between the lumen 300 ofthe vessel 250 to be processed and the lumen 304 of the processingvessel 296 via the restricted opening 294 is at least substantially leakproof.

V.B. As a further option, either or both of the Luer lock fittings 332and 334 can be made of electrically conductive material, for examplestainless steel. This construction material forming or adjacent to therestricted opening 294 might contribute to formation of the plasma inthe restricted opening 294.

V.B. The desirable volume of the lumen 304 of the processing vessel 296is contemplated to be a trade-off between a small volume that will notdivert much of the reactant flow away from the product surfaces desiredto be coated and a large volume that will support a generous reactantgas flow rate through the restricted opening 294 before filling thelumen 304 sufficiently to reduce that flow rate to a less desirablevalue (by reducing the pressure difference across the restricted opening294). The contemplated volume of the lumen 304, in an embodiment, isless than three times the volume of the lumen 300 of the vessel 250 tobe processed, or less than two times the volume of the lumen 300 of thevessel 250 to be processed, or less than the volume of the lumen 300 ofthe vessel 250 to be processed, or less than 50% of the volume of thelumen 300 of the vessel 250 to be processed, or less than 25% of thevolume of the lumen 300 of the vessel 250 to be processed. Othereffective relationships of the volumes of the respective lumens are alsocontemplated.

V.B. The inventors have found that the uniformity of coating can beimproved in certain embodiments by repositioning the distal end of theelectrode 308 relative to the vessel 250 so it does not penetrate as farinto the lumen 300 of the vessel 250 as the position of the innerelectrode shown in previous Figures. For example, although in certainembodiments the distal opening 316 can be positioned adjacent to therestricted opening 294, in other embodiments the distal opening 316 canbe positioned less than ⅞ the distance, optionally less than ¾ thedistance, optionally less than half the distance to the restrictedopening 294 from the larger opening 302 of the vessel to be processedwhile feeding the reactant gas. Or, the distal opening 316 can bepositioned less than 40%, less than 30%, less than 20%, less than 15%,less than 10%, less than 8%, less than 6%, less than 4%, less than 2%,or less than 1% of the distance to the restricted opening 294 from thelarger opening of the vessel to be processed while feeding the reactantgas.

V.B. Or, the distal end of the electrode 308 can be positioned eitherslightly inside or outside or flush with the larger opening 302 of thevessel 250 to be processed while communicating with, and feeding thereactant gas to, the interior of the vessel 250. The positioning of thedistal opening 316 relative to the vessel 250 to be processed can beoptimized for particular dimensions and other conditions of treatment bytesting it at various positions. One particular position of theelectrode 308 contemplated for treating syringe barrels 250 is with thedistal end 314 penetrating about a quarter inch (about 6 mm) into thevessel lumen 300 above the larger opening 302.

V.B. The inventors presently contemplate that it is advantageous toplace at least the distal end 314 of the electrode 308 within the vessel250 so it will function suitably as an electrode, though that is notnecessarily a requirement. Surprisingly, the plasma 318 generated in thevessel 250 can be made more uniform, extending through the restrictedopening 294 into the processing vessel lumen 304, with less penetrationof the electrode 308 into the lumen 300 than has previously beenemployed. With other arrangements, such as processing a closed-endedvessel, the distal end 314 of the electrode 308 commonly is placedcloser to the closed end of the vessel than to its entrance.

V.B. Or, the distal end 314 of the electrode 308 can be positioned atthe restricted opening 294 or beyond the restricted opening 294, forexample within the processing vessel lumen 304, as illustrated forexample in FIG. 33. Various expedients can optionally be provided, suchas shaping the processing vessel 296 to improve the gas flow through therestricted opening 294.

V.B. As another alternative, illustrated in FIGS. 34-35, the compositeinner electrode and gas supply tube 398 can have distal gas supplyopenings such as 400, optionally located near the larger opening 302,and an extension electrode 402 extending distal of the distal gas supplyopenings 400, optionally extending to a distal end adjacent to therestricted opening 294, and optionally further extending into theprocessing vessel 324. This construction is contemplated to facilitateformation of plasma within the inner surface 292 adjacent to therestricted opening 294.

V.B. In yet another contemplated embodiment, the inner electrode 308, asin FIG. 26, can be moved during processing, for example, at firstextending into the processing vessel lumen 304, then being withdrawnprogressively proximally as the process proceeds. This expedient isparticularly contemplated if the vessel 250, under the selectedprocessing conditions, is long, and movement of the inner electrodefacilitates more uniform treatment of the interior surface 254. Usingthis expedient, the processing conditions, such as the gas feed rate,the vacuum draw rate, the electrical energy applied to the outerelectrode 160, the rate of withdrawing the inner electrode 308, or otherfactors can be varied as the process proceeds, customizing the processto different parts of a vessel to be treated.

V.B. Conveniently, as in the other processes described in thisspecification, the larger opening of the generally tubular vessel 250 tobe processed can be placed on a vessel support 320, as by seating thelarger opening 302 of the vessel 250 to be processed on a port 322 ofthe vessel support 320. Then the inner electrode 308 can be positionedwithin the vessel 250 seated on the vessel support 320 before drawing atleast a partial vacuum within the lumen 300 of the vessel 250 to beprocessed.

V.B. In an alternative embodiment, illustrated in FIG. 28, theprocessing vessel 324 can be provided in the form of a conduit having afirst opening 306 secured to the vessel 250 to be processed, as shown inFIG. 26, and a second opening 328 communicating with a vacuum port 330in the vessel support 320. In this embodiment, the PECVD process gasescan flow into the vessel 250, then via the restricted opening 294 intothe processing vessel 324, then return via the vacuum port 330.Optionally, the vessel 250 can be evacuated through both openings 294and 302 before applying the PECVD reactants.

V.B. Or, an uncapped syringe barrel 250, as shown in FIG. 22, can beprovided with an interior coating SiO_(x), in which x in this formula isfrom about 1.5 to about 2.9, alternatively from about 1.5 to about 2.6,alternatively about 2, barrier or other type of PECVD coating byintroducing the reactants from the source 144 through the opening at theback end 256 of the barrel 250 and drawing a vacuum using the vacuumsource 98 drawing through the opening at the front end 260 of thebarrel. For example, the vacuum source 98 can be connected through asecond fitting 266 seated on the front end 260 of the syringe barrel250. Using this expedient, the reactants can flow through the barrel 250in a single direction (upward as shown in FIG. 22, though theorientation is not critical), and there is no need to convey thereactants through a probe that separates the fed gas from the exhaustedgas within the syringe barrel 250. The front and back ends 260 and 256of the syringe barrel 250 can also be reversed relative to the coatingapparatus, in an alternative arrangement. The probe 108 can act simplyas an electrode, and can either be tubular or a solid rod in thisembodiment. As before, the separation between the interior surface 254and the probe 108 can be uniform over at least most of the length of thesyringe barrel 250.

V.B. FIG. 37 is a view similar to FIG. 22 showing another embodiment inwhich the fitting 266 is independent of and not attached to the plateelectrodes 414 and 416. The fitting 266 can have a Luer lock fittingadapted to be secured to the corresponding fitting of the syringe barrel250. This embodiment allows the vacuum conduit 418 to pass over theelectrode 416 while the vessel holder 420 and attached vessel 250 movebetween the electrodes 414 and 416 during a coating step.

V.B. FIG. 38 is a view similar to FIG. 22 showing still anotherembodiment in which the front end 260 of the syringe barrel 250 is openand the syringe barrel 250 is enclosed by a vacuum chamber 422 seated onthe vessel holder 424. In this embodiment the pressures P1 within thesyringe barrel 250 and within the vacuum chamber 422 are approximatelyidentical, and the vacuum in the vacuum chamber 422 optionally is drawnthrough the front end 260 of the syringe barrel 250. When the processgases flow into the syringe barrel 250, they flow through the front end260 of the syringe barrel 250 until a steady composition is providedwithin the syringe barrel 250, at which time the electrode 160 isenergized to form the coating. It is contemplated that due to the largervolume of the vacuum chamber 422 relative to the syringe barrel 250, andthe location of the counter electrode 426 within the syringe barrel 250,the process gases passing through the front end 260 will not formsubstantial deposits on the walls of the vacuum chamber 422.

V.B. FIG. 39 is a view similar to FIG. 22 showing yet another embodimentin which the back flange of the syringe barrel 250 is clamped between avessel holder 428 and an electrode assembly 430 to which a cylindricalelectrode or pair of plate electrodes indicated as 160 and a vacuumsource 98 are secured. The volume generally indicated as 432 enclosedoutside the syringe barrel 250 is relatively small in this embodiment tominimize the pumping needed to evacuate the volume 432 and the interiorof the syringe barrel 250 to operate the PECVD process.

V.B. FIG. 40 is a view similar to FIG. 22 and FIG. 41 is a plan viewshowing even another embodiment as an alternative to FIG. 38 in whichthe ratio of pressures P1/P2 is maintained at a desired level byproviding a pressure proportioning valve 434. It is contemplated that P1can be a lower vacuum, i.e. a higher pressure, than P2 during a PECVDprocess so the waste process gases and by-products will pass through thefront end 260 of the syringe barrel 250 and be exhausted. Also, theprovision of a separate vacuum chamber conduit 436 to serve the vacuumchamber 422 allows the use of a separate vacuum pump to evacuate thegreater enclosed volume 432 more quickly.

V.B. FIG. 41 is a plan view of the embodiment of FIG. 40, also showingthe electrode 160 removed from FIG. 40.

V.C. Method of Applying a Lubricity Layer

V.C. Another embodiment is a method of applying a lubricity layerderived from an organosilicon precursor. A “lubricity layer” or anysimilar term is generally defined as a coating that reduces thefrictional resistance of the coated surface, relative to the uncoatedsurface. If the coated object is a syringe (or syringe part, e.g.syringe barrel) or any other item generally containing a plunger ormovable part in sliding contact with the coated surface, the frictionalresistance has two main aspects—breakout force and plunger slidingforce.

The plunger sliding force test is a specialized test of the coefficientof sliding friction of the plunger within a syringe, accounting for thefact that the normal force associated with a coefficient of slidingfriction as usually measured on a flat surface is addressed bystandardizing the fit between the plunger or other sliding element andthe tube or other vessel within which it slides. The parallel forceassociated with a coefficient of sliding friction as usually measured iscomparable to the plunger sliding force measured as described in thisspecification. Plunger sliding force can be measured, for example, asprovided in the ISO 7886-1:1993 test.

The plunger sliding force test can also be adapted to measure othertypes of frictional resistance, for example the friction retaining astopper within a tube, by suitable variations on the apparatus andprocedure. In one embodiment, the plunger can be replaced by a closureand the withdrawing force to remove or insert the closure can bemeasured as the counterpart of plunger sliding force.

Also or instead of the plunger sliding force, the breakout force can bemeasured. The breakout force is the force required to start a stationaryplunger moving within a syringe barrel, or the comparable force requiredto unseat a seated, stationary closure and begin its movement. Thebreakout force is measured by applying a force to the plunger thatstarts at zero or a low value and increases until the plunger beginsmoving. The breakout force tends to increase with storage of a syringe,after the prefilled syringe plunger has pushed away the interveninglubricant or adhered to the barrel due to decomposition of the lubricantbetween the plunger and the barrel. The breakout force is the forceneeded to overcome “sticktion,” an industry term for the adhesionbetween the plunger and barrel that needs to be overcome to break outthe plunger and allow it to begin moving.

V.C. Some utilities of coating a vessel in whole or in part with alubricity layer, such as selectively at surfaces contacted in slidingrelation to other parts, is to ease the insertion or removal of astopper or passage of a sliding element such as a piston in a syringe ora stopper in a sample tube. The vessel can be made of glass or a polymermaterial such as polyester, for example polyethylene terephthalate(PET), a cyclic olefin copolymer (COC), an olefin such as polypropylene,or other materials. Applying a lubricity layer by PECVD can avoid orreduce the need to coat the vessel wall or closure with a sprayed,dipped, or otherwise applied organosilicon or other lubricant thatcommonly is applied in a far larger quantity than would be deposited bya PECVD process.

V.C. In any of the above embodiments V.C., a plasma, optionally anon-hollow-cathode plasma, optionally can be formed in the vicinity ofthe substrate

V.C. In any of embodiments V.C., the precursor optionally can beprovided in the substantial absence of oxygen. V.C. In any ofembodiments V.C., the precursor optionally can be provided in thesubstantial absence of a carrier gas. V.C. In any of embodiments V.C.,in which the precursor optionally can be provided in the substantialabsence of nitrogen. V.C. In any of embodiments V.C., in which theprecursor optionally can be provided at less than 1 Torr absolutepressure.

V.C. In any of embodiments V.C., the precursor optionally can beprovided to the vicinity of a plasma emission.

V.C. In any of embodiments V.C., the coating optionally can be appliedto the substrate at a thickness of 1 to 5000 nm, or 10 to 1000 nm, or10-200 nm, or 20 to 100 nm thick. The thickness of this and othercoatings can be measured, for example, by transmission electronmicroscopy (TEM).

V.C. The TEM can be carried out, for example, as follows. Samples can beprepared for Focused Ion Beam (FIB) cross-sectioning in two ways. Eitherthe samples can be first coated with a thin layer of carbon (50-100 nmthick) and then coated with a sputtered layer of platinum (50-100 nmthick) using a K575X Emitech coating system, or the samples can becoated directly with the protective sputtered Pt layer. The coatedsamples can be placed in an FEI FIB200 FIB system. An additional layerof platinum can be FIB-deposited by injection of an oregano-metallic gaswhile rastering the 30 kV gallium ion beam over the area of interest.The area of interest for each sample can be chosen to be a location halfway down the length of the syringe barrel. Thin cross sections measuringapproximately 15 .mu.m (“micrometers”) long, 2 .mu.m wide and 15 .mu.mdeep can be extracted from the die surface using a proprietary in-situFIB lift-out technique. The cross sections can be attached to a 200 meshcopper TEM grid using FIB-deposited platinum. One or two windows in eachsection, measuring .about.8 .mu.m wide, can be thinned to electrontransparency using the gallium ion beam of the FEI FIB.

V.C. Cross-sectional image analysis of the prepared samples can beperformed utilizing either a Transmission Electron Microscope (TEM), ora Scanning Transmission Electron Microscope (STEM), or both. All imagingdata can be recorded digitally. For STEM imaging, the grid with thethinned foils can be transferred to a Hitachi HD2300 dedicated STEM.Scanning transmitted electron images can be acquired at appropriatemagnifications in atomic number contrast mode (ZC) and transmittedelectron mode (TE). The following instrument settings can be used.

1. Instrument Scanning Transmission Electron MicroscopeManufacturer/Model Hitachi HD2300 Accelerating Voltage 200 kV ObjectiveAperture #2 Condenser Lens 1 Setting 1.672 Condenser Lens 2 Setting1.747 Approximate Objective Lens Setting 5.86 ZC Mode Projector Lens1.149 TE Mode Projector Lens 0.7 Image Acquisition Pixel Resolution 1280× 960 Acquisition Time 20 sec.(×4)

V.C. For TEM analysis the sample grids can be transferred to a HitachiHF2000 transmission electron microscope. Transmitted electron images canbe acquired at appropriate magnifications. The relevant instrumentsettings used during image acquisition can be those given below.

Instrument Transmission Electron Microscope Manufacturer/Model HitachiHF2000 Accelerating Voltage 200 kV Condenser Lens 1 0.78 Condenser Lens2 0 Objective Lens 6.34 Condenser Lens Aperture #1 Objective LensAperture for #3 imaging Selective Area Aperture for SAD N/A

V.C. In any of embodiments V.C., the substrate can comprise glass or apolymer, for example a polycarbonate polymer, an olefin polymer, acyclic olefin copolymer, a polypropylene polymer, a polyester polymer, apolyethylene terephthalate polymer or a combination of any two or moreof these.

V.C. In any of embodiments V.C., the PECVD optionally can be performedby energizing the gaseous reactant containing the precursor withelectrodes powered at a RF frequency as defined above, for example afrequency from 10 kHz to less than 300 MHz, optionally from 1 to 50 MHz,even optionally from 10 to 15 MHz, optionally a frequency of 13.56 MHz.

V.C. In any of embodiments V.C., the plasma can be generated byenergizing the gaseous reactant comprising the precursor with electrodessupplied with electric power sufficient to form a lubricity layer.Optionally, the plasma is generated by energizing the gaseous reactantcontaining the precursor with electrodes supplied with an electric powerof from 0.1 to 25 W, optionally from 1 to 22 W, optionally from 3 to 17W, even optionally from 5 to 14 W, optionally from 7 to 11 W, optionally8 W. The ratio of the electrode power to the plasma volume can be lessthan 10 W/ml, optionally is from 5 W/ml to 0.1 W/ml, optionally is from4 W/ml to 0.1 W/ml, optionally from 2 W/ml to 0.2 W/ml. These powerlevels are suitable for applying lubricity coatings to syringes andsample tubes and vessels of similar geometry having a void volume of 1to 3 mL in which PECVD plasma is generated. It is contemplated that forlarger or smaller objects the power applied should be increased orreduced accordingly to scale the process to the size of the substrate.

V.C. One contemplated product optionally can be a syringe having abarrel treated by the method of any one or more of embodiments V.C.

V.D. Liquid-Applied Coatings

V.D. Another example of a suitable barrier or other type of coating,usable in conjunction with PECVD-applied coatings or other PECVDtreatment as disclosed here, can be a liquid barrier, lubricant, surfaceenergy tailoring, or other type of coating 90 applied to the interiorsurface of a vessel, either directly or with one or more interveningPECVD-applied coatings described in this specification, for exampleSiO_(x), a lubricity layer characterized as defined in the DefinitionSection, or both.

V.D. Suitable liquid barriers or other types of coatings 90 alsooptionally can be applied, for example, by applying a liquid monomer orother polymerizable or curable material to the interior surface of thevessel 80 and curing, polymerizing, or crosslinking the liquid monomerto form a solid polymer. Suitable liquid barrier or other types ofcoatings 90 can also be provided by applying a solvent-dispersed polymerto the surface 88 and removing the solvent.

V.D. Either of the above methods can include as a step forming a coating90 on the interior 88 of a vessel 80 via the vessel port 92 at aprocessing station or device 28. One example is applying a liquidcoating, for example of a curable monomer, prepolymer, or polymerdispersion, to the interior surface 88 of a vessel 80 and curing it toform a film that physically isolates the contents of the vessel 80 fromits interior surface 88. The prior art describes polymer coatingtechnology as suitable for coating plastic blood collection tubes. Forexample, the acrylic and polyvinylidene chloride (PVdC) coatingmaterials and coating methods described in U.S. Pat. No. 6,165,566,which is hereby incorporated by reference, optionally can be used.

V.D. Either of the above methods can also or include as a step forming acoating on the exterior outer wall of a vessel 80. The coatingoptionally can be a barrier layer, optionally an oxygen barrier layer,or optionally a water barrier layer. One example of a suitable coatingis polyvinylidene chloride, which functions both as a water barrier andan oxygen barrier. Optionally, the barrier layer can be applied as awater-based coating. The coating optionally can be applied by dippingthe vessel in it, spraying it on the vessel, or other expedients. Avessel having an exterior barrier layer as described above is alsocontemplated.

VI. Vessel Inspection

VI. One station or device shown in FIG. 1 is the processing station ordevice 30, which can be configured to inspect the interior surface of avessel 80 for defects, as by measuring the air pressure loss or massflow rate or volume flow rate through a vessel wall or outgassing of avessel wall. The device 30 can operate similarly to the device 26,except that better performance (less leakage or permeation at givenprocess conditions) can be required of the vessel to pass the inspectionprovided by the device 30, since in the illustrated embodiment a barrieror other type of coating has been applied by the station or device 28before the station or device 30 is reached. In an embodiment, thisinspection of the coated vessel 80 can be compared to the inspection ofthe same vessel 80 at the device or station 26. Less leakage orpermeation at the station or device 30 indicates that the barrier layeris functioning at least to a degree.

VI. The identity of a vessel 80 measured at two different stations or bytwo different devices can be ascertained by placing individualidentifying characteristics, such as a bar code, other marks, or a radiofrequency identification (RFID) device or marker, on each of the vesselholders 38-68 and matching up the identity of vessels measured at two ormore different points about the endless conveyor shown in FIG. 1. Sincethe vessel holders can be reused, they can be registered in a computerdatabase or other data storage structure as they reach the position ofthe vessel holder 40 in FIG. 1, just after a new vessel 80 has beenseated on the vessel holder 40, and removed from the data register at ornear the end of the process, for example as or after they reach theposition of the vessel holder 66 in FIG. 1 and the processed vessel 80is removed by the transfer mechanism 74.

VI. The processing station or device 32 can be configured to inspect avessel, for example a barrier or other type of coating applied to thevessel, for defects. In the illustrated embodiment, the station ordevice 32 determines the optical source transmission of the coating, asa measurement of the thickness of the coating. The barrier or other typeof coating, if suitably applied, can make the vessel 80 moretransparent, even though additional material has been applied.

VI. Other measures of the thickness of the coating are alsocontemplated, as by using interference measurements to determine thedifference in travel distance between an energy wave that bounces offthe inside of the coating 90 (interfacing with the atmosphere within thevessel interior 154) and an energy wave that bounces off the interiorsurface 88 of the vessel 80 (interfacing with the outside of the coating90). As is well known, the difference in travel distance can bedetermined directly, as by measuring the time of arrival of therespective waves with high precision, or indirectly, as by determiningwhat wavelengths of the incident energy are reinforced or canceled, inrelation to the test conditions.

VI. Another measurement technique that can be carried out to checkcoating integrity is an ellipsometric measurement on the device. In thiscase, a polarized laser beam can be projected either from the inside orthe outside of the vessel 80. In the case of a laser beam projected fromthe inside, the laser beam can be pointed orthogonally at the surfaceand then either the transmitted or reflected beam can be measured. Thechange in beam polarity can be measured. Since a coating or treatment onthe surface of the device will impact (change) the polarization of thelaser beam, changes in the polarity can be the desired result. Thechanges in the polarity are a direct result of the existence of acoating or treatment on the surface and the amount of change is relatedto the amount of treatment or coating.

VI. If the polarized beam is projected from the outside of the device, adetector can be positioned on the inside to measure the transmittedcomponent of the beam (and the polarity determined as above). Or, adetector can be placed outside of the device in a position that cancorrespond to the reflection point of the beam from the interfacebetween the treatment/coating (on the inside of the device). Thepolarity change(s) can then be determined as detailed above.

VI. In addition to measuring properties as described above, other probesand/or devices can be inserted into the inside of the device andmeasurements made with a detector apparatus. This apparatus is notlimited by the measurement technique or method. Other test methods thatemploy mechanical, electrical, or magnetic properties, or any otherphysical, optical, or chemical property, can be utilized.

VI. During the plasma treatment setup, an optical detection systemoptionally can be used to record the plasma emission spectrum(wavelength and intensity profile), which corresponds to the uniquechemical signature of the plasma environment. This characteristicemission spectrum provides evidence that the coating has been applied.The system also offers a real-time precision measurement and dataarchive tool for each part processed.

VI. Any of the above methods can include as a step inspecting theinterior surface 88 of a vessel 80 for defects at a processing stationsuch as 24, 26, 30, 32, or 34. Inspecting can be carried out, as at thestations 24, 32, and 34, by inserting a detection probe 172 into thevessel 80 via the vessel port 92 and detecting the condition of thevessel interior surface 88 or a barrier or other type of coating 90using the probe 172. Inspecting can be carried out, as shown in FIG. 11,by radiating energy inward through the vessel wall 86 and vesselinterior surface 88 and detecting the energy with the probe 172. Or,inspecting can be carried out by reflecting the radiation from thevessel interior surface 88 and detecting the energy with a detectorlocated inside the vessel 80. Or, inspecting can be carried out bydetecting the condition of the vessel interior surface 88 at numerous,closely spaced positions on the vessel interior surface.

VI. Any of the above methods can include carrying out the inspectingstep at a sufficient number of positions throughout the vessel interiorsurface 88 to determine that the barrier or other type of coating 90will be effective to prevent the pressure within the vessel, when it isinitially evacuated and its wall is exposed to the ambient atmosphere,from increasing to more than 20% of the ambient atmospheric pressureduring a shelf life of a year.

VI. Any of the above methods can include carrying out the inspectingstep within an elapsed time of 30 or fewer seconds per vessel, or 25 orfewer seconds per vessel, or 20 or fewer seconds per vessel, or 15 orfewer seconds per vessel, or 10 or fewer seconds per vessel, or 5 orfewer seconds per vessel, or 4 or fewer seconds per vessel, or 3 orfewer seconds per vessel, or 2 or fewer seconds per vessel, or 1 orfewer seconds per vessel. This can be made possible, for example, bymeasuring the efficacy of the barrier or other type of coated vesselwall, as shown in FIG. 7, which can involve one measurement for theentire vessel 80, or by inspecting many or even all the points to beinspected in parallel, as by using the charge coupled device as thedetector 172 shown or substitutable in FIGS. 6, 10, and 11. The latterstep can be used for detecting the condition of the barrier or othertype of coating at numerous, closely spaced positions on the vesselinterior surface 88 in a very short overall time.

VI. In any embodiment of the method, a multi-point vessel inspection canbe further expedited, if desired, by collecting data using a chargecoupled device 172, transporting away the vessel 80 that has just beeninspected, and processing the collected data shortly thereafter, whilethe vessel 80 is moving downstream. If a defect in the vessel 80 islater ascertained due to the data processing, the vessel 80 that isdefective can be moved off line at a point downstream of the detectionstation such as 34 (FIG. 10).

VI. In any of the above embodiments, the inspecting step can be carriedout at a sufficient number of positions throughout the vessel 80interior surface 88 to determine that the barrier or other type ofcoating 90 will be effective to prevent the initial vacuum level (i.e.initial reduction of pressure versus ambient) within the vessel 80, whenit is initially evacuated and its wall 86 is exposed to the ambientatmosphere, from decreasing more than 20%, optionally more than 15%,optionally more than 10%, optionally more than 5%, optionally more than2%, during a shelf life of at least 12 months, or at least 18 months, orat least two years.

VI. The initial vacuum level can be a high vacuum, i.e. a remainingpressure of less than 10 Torr, or a lesser vacuum such as less than 20Torr of positive pressure (i.e. the excess pressure over a full vacuum),or less than 50 Torr, or less than 100 Torr, or less than 150 Torr, orless than 200 Torr, or less than 250 Torr, or less than 300 Torr, orless than 350 Torr, or less than 380 Torr of positive pressure. Theinitial vacuum level of evacuated blood collection tubes, for example,is in many instances determined by the type of test the tube is to beused for, and thus the type and appropriate amount of a reagent that isadded to the tube at the time of manufacture. The initial vacuum levelis commonly set to draw the correct volume of blood to combine with thereagent charge in the tube.

VI. In any of the above embodiments, the barrier or other type ofcoating 90 inspecting step can be carried out at a sufficient number ofpositions throughout the vessel interior surface 88 to determine thatthe barrier or other type of coating 90 will be effective to prevent thepressure within the vessel 80, when it is initially evacuated and itswall is exposed to the ambient atmosphere, from increasing to more than15%, or more than 10%, of the ambient atmospheric pressure of theambient atmospheric pressure during a shelf life of at least one year.

VI.A. Vessel Processing Including Pre-Coating and Post-CoatingInspection

VI.A. Even another embodiment is a vessel processing method forprocessing a molded plastic vessel having an opening and a wall definingan interior surface. The method is carried out by inspecting theinterior surface of the vessel as molded or just before coating fordefects; applying a coating to the interior surface of the vessel afterinspecting the vessel as molded; and inspecting the coating for defects.

VI.A. Another embodiment is a vessel processing method in which abarrier layer is applied to the vessel after inspecting the vessel asmolded, and the interior surface of the vessel is inspected for defectsafter applying the barrier layer.

VI.A. In an embodiment, the station or device 26 (which can alsofunction as the station or device 28 for applying a coating) can be usedas follows for barometric vessel inspection. With either or both of thevalves 136 and 148 open, the vessel 80 can be evacuated to a desireddegree, optionally to a very low pressure such as less than 10 Torr,optionally less than 1 Torr. Whichever of the valves 136 and 148 isinitially open can then be closed, isolating the evacuated interior 154of the vessel 80 and the pressure gauge 152 from ambient conditions andfrom the vacuum source 98. The change in pressure over a measurementtime, whether due to the ingress of gas through the vessel wall oroutgassing from the material of the wall and/or a coating on the vesselwall, can then be sensed and used to calculate the rate of ingress ofambient gas into the vessel 80 as mounted on the vessel holder 44. Forthe present purpose, outgassing is defined as the release of adsorbed oroccluded gases or water vapor from the vessel wall, optionally in atleast a partial vacuum.

VI.A. Another optional modification can be to provide the ambient gas ata higher pressure than atmospheric pressure. This again can increase therate of gas transfer through a barrier or other type of layer, providinga measurable difference in a shorter time than if a lower ambientpressure were provided. Or, gas can be introduced into the vessel 80 ata higher than atmospheric pressure, again increasing the transfer ratethrough the wall 86.

VI.A. Optionally, the vessel inspection at the station or by the device26 can be modified by providing an inspection gas, such as helium, on anupstream side with respect to the substrate, either within or outsidethe vessel 80, and detecting it on the downstream side. Alow-molecular-weight gas, such as hydrogen, or a less expensive or moreavailable gas, such as oxygen or nitrogen, can also be used as aninspection gas.

VI.A. Helium is contemplated as an inspection gas that can increase therate of leak or permeation detection, as it will pass through animperfect barrier or other type of coating, or past a leaking seal, muchmore quickly than the usual ambient gases such as nitrogen and oxygen inordinary air. Helium has a high transfer rate through many solidsubstrates or small gaps because it: (1) is inert, so it is not adsorbedby the substrate to any great degree, (2) is not ionized easily, so itsmolecules are very compact due to the high level of attraction betweenits electrons and nucleus, and (3) has a molecular weight of 4, asopposed to nitrogen (molecular weight 28) and oxygen (molecular weight32), again making the molecules more compact and easily passed through aporous substrate or gap. Due to these factors, helium will travelthrough a barrier having a given permeability much more quickly thanmany other gases. Also, the atmosphere contains an extremely smallproportion of helium naturally, so the presence of additional helium canbe relatively easy to detect, particularly if the helium is introducedwithin the vessel 80 and detected outside the vessel 80 to measureleakage and permeation. The helium can be detected by a pressure dropupstream of the substrate or by other means, such as spectroscopicanalysis of the downstream gas that has passed through the substrate.

VI.A. An example of barometric vessel inspection by determining theoxygen concentration from O₂ fluorescence detection follows.

VI.A. An Excitation Source (Ocean Optics USB-LS-450 Pulsed Blue LED),fiber assembly (Ocean Optics QBIF6000-VIS-NIR), a spectrometer(USB4000-FL Fluorescence Spectrometer), an oxygen sensor probe (OceanOptics FOXY-R), and a vacuum feed through adaptor (likeVFT-1000-VIS-275) connected to a vacuum source are used. A vacuum can beapplied to remove the ambient air, and when the vessel is at a definedpressure any oxygen content that has leaked or permeated in to refillthe vessel from the ambient air can be determined using the detectionsystem. A coated tube replaces the uncoated tube and O₂ concentrationmeasurement can be taken. The coated tube will demonstrate reproduciblydifferent atmospheric oxygen content than the uncoated sample due todifferential O₂ surface absorption on the coated tube (an SiO_(x)surface, versus the uncoated PET or glass surface) and/or a change in O₂diffusion rate from the surface. Detection time can be less than onesecond.

VI.A. These barometric methods should not be considered limited to aspecific gas sensed (helium detection or other gases can be considered)or a specific apparatus or arrangement.

VI.A. The processing station or device 34 also can be configured toinspect a barrier or other type of coating for defects. In theembodiment of FIGS. 1 and 10, the processing station or device 34 can beanother optical inspection, this time intended to scan or separatelymeasure the properties of at least a portion of the barrier or othertype of coating 90, or substantially the entire barrier or other type ofcoating 90, at numerous, closely spaced positions on the barrier orother type of coating 90. The numerous, closely spaced positions can be,for example, spaced about 1 micron apart, or about 2 microns apart, orabout 3 microns apart, or about 4 microns apart, or about 5 micronsapart, or about 6 microns apart, or about 7 microns apart, either inevery case or on average over at least part of the surface, thusseparately measuring some or all small portions of the barrier or othertype of coating 90. In an embodiment, a separate scan of each small areaof the coating can be useful to find individual pinholes or otherdefects, and to distinguish the local effects of pinhole defects frommore general defects, such as a large area with a coating that is toothin or porous.

VI.A. The inspection by the station or device 34 can be carried out byinserting a radiation or light source 170 or any other suitable radiofrequency, microwave, infrared, visible light, ultraviolet, x-ray, orelectron beam source, for example, into the vessel 80 via the vesselport 92 and detecting the condition of the vessel interior surface, forexample the barrier layer 90, by detecting radiation transmitted fromthe radiation source using a detector.

VI.A. The above vessel holder system can also be used for testing thedevice. For example, the probe 108 of FIG. 2 having a gas delivery port110 can be replaced by a light source 170 (FIG. 10). The light source170 can irradiate the inside of the tube and then subsequent testing canbe completed outside of the tube, measuring transmission or otherproperties. The light source 170 can be extended into the inside of thetube in the same manner that the probe 108 is pushed into the puck orvessel holder 62, although a vacuum and seals are not necessarilyrequired. The light source 170 can be an optical fiber source, a laser,a point (such as an LED) source or any other radiation source. Thesource can radiate at one or more frequencies from the deep UV (100 nm)into the far infrared (100 microns) and all frequencies in between.There is no limitation on the source that can be used.

VI.A. As a specific example see FIG. 10. In FIG. 10 the tube or vessel80 is positioned in the puck or vessel holder 62 and a light source 170at the end of the probe 108 has been inserted into the tube. The lightsource 170 in this case can be a blue LED source of sufficient intensityto be received by the detector 172 surrounding the outside of the vessel80. The light source 170 can be, for example, a three dimensionalcharge-coupled-device (CCD) comprising an array of pixels such as 174 onits interior surface 176. The pixels such as 174 receive and detect theillumination radiated through the barrier or other type of coating 90and vessel wall 86. In this embodiment the detector 172 has a largerinner diameter relative to the vessel 80 than the separation of theelectrode 164 and vessel 80 of FIG. 2, and has a cylindrical top portionadjacent to the closed end 84 instead of a hemispherical top portion.The outside detector 172 or can have a smaller radial gap from thevessel 80 and a gap of more uniform dimension at its top portionadjacent to the closed end 84. This can be accomplished, for example, byproviding a common center of curvature for the closed end 84 and the topof the detector 172 when the vessel 80 is seated. This variation mightprovide more uniform inspection of the curved closed end 84 of thevessel 80, although either variation is contemplated to be suitable.

VI.A. Prior to the light source being turned on, the CCD is measured andthe resulting value stored as a background (which can be subtracted fromsubsequent measurements). The light source 170 is then turned on andmeasurements taken with the CCD. The resulting measurements can then beused to compute total light transmission (and compared to an uncoatedtube to determine the average coating thickness) and defect density (bytaking individual photon counts on each element of the CCD and comparingthem to a threshold value—if the photon count is lower, then thiscorresponds to not enough light being transmitted). Low lighttransmission likely is the result of no or too-thin coating—a defect inthe coating on the tube. By measuring the number of adjacent elementsthat have a low photon count, the defect size can be estimated. Bysumming the size and number of defects, the tube's quality can beassessed, or other properties determined that might be specific to thefrequency of the radiation from the light source 170.

VI.A. In the embodiment of FIG. 10, energy can be radiated outwardthrough the vessel interior surface, such as through the coating 90 andthe vessel wall 86, and detected with a detector 172 located outside thevessel. Various types of detectors 172 can be used.

VI.A. Since the incident radiation from the source 170 transmittedthrough the barrier or other type of coating 90 and vessel wall 80 canbe greater for a lower angle of incidence (compared to a reference linenormal to the vessel wall 80 at any given point), the pixels such as 174lying on a normal line through the vessel wall 86 will receive more ofthe radiation than neighboring pixels, though more than one pixel canreceive some of the light passing through a given portion of the barrieror other type of coating, and the light passing through more than onegiven portion of the barrier or other type of coating 90 and vessel wall80 will be received by a particular pixel such as 174.

VI.A. The degree of resolution of the pixels such as 174 for detectingradiation passing through a particular portion of the barrier or othertype of coating 90 and vessel wall 86 can be increased by placing theCCD so its array of pixels such as 174 is very close to and closelyconforms to the contours of the vessel wall 86. The degree of resolutioncan also be increased by selecting a smaller or essentially point sourceof light, as shown diagrammatically in FIG. 6, to illuminate theinterior of the vessel 80. Using smaller pixels will also improve theresolution of the array of pixels in the CCD.

VI.A. In FIG. 6 a point light source 132 (laser or LED) is positioned atthe end of a rod or probe. (“Point source” refers either to lightemanating from a small-volume source resembling a mathematical point, ascan be generated by a small LED or a diffusing tip on an optical fiberradiating light in all directions, or to light emanated as asmall-cross-section beam, such as coherent light transmitted by alaser.) The point source of light 132 can be either stationary ormovable, for example axially movable, while the characteristics of thebarrier or other type of coating 90 and vessel wall 80 are beingmeasured. If movable, the point light source 132 can be moved up anddown inside of the device (tube) 80. In a similar manner describedabove, the interior surface 88 of the vessel 80 can be scanned andsubsequent measurements made by an external detector apparatus 134 todetermine coating integrity. An advantage of this approach is that alinearly polarized or similar coherent light source with specificdirectionality can be used.

VI.A. The position of the point source of light 132 can be indexed tothe pixels such as 174 so the illumination of the detectors can bedetermined at the time the detector is at a normal angle with respect toa particular area of the coating 90. In the embodiment of FIG. 10, acylindrical detector 172, optionally with a curved end matching thecurve (if any) of the closed end 84 of a vessel 80, can be used todetect the characteristics of a cylindrical vessel 80.

VI.A. It will be understood, with reference to FIG. 10, that theinspection station or device 24 or 34 can be modified by reversing thepositions of the light or other radiation source 170 and detector 172 sothe light radiates through the vessel wall 86 from the exterior to theinterior of the vessel 80. If this expedient is selected, in anembodiment a uniform source of incident light or other radiation can beprovided by inserting the vessel 80 into an aperture 182 through thewall 184 of an integrating sphere light source 186. An integratingsphere light source will disperse the light or radiation from the source170 outside the vessel 80 and inside the integrating sphere, so thelight passing through the respective points of the wall 86 of the vessel80 will be relatively uniform. This will tend to reduce the distortionscaused by artifacts relating to portions of the wall 86 having differentshapes.

VI.A. In the embodiment of FIG. 11, the detector 172 can be shown toclosely conform to the barrier or other type of coating 90 or interiorsurface 88 of the vessel 80. Since the detector 172 can be on the sameside of the vessel wall 86 as the barrier or other type of coating 80,this proximity will tend to increase the resolution of the pixels suchas 174, though in this embodiment the detector 172 optionally will beprecisely positioned relative to the barrier or other type of coating 90to avoid scraping one against the other, possibly damaging either thecoating or the CCD array. Placing the detector 172 immediately adjacentto the coating 90 also can reduce the effects of refraction by thevessel wall 86, which in the embodiment of FIG. 10 occurs after thelight or other radiation passes through the barrier or other type ofcoating 90, so the signal to be detected can be differentially refracteddepending on the local shape of the vessel 80 and the angle of incidenceof the light or other radiation.

VI.A. Other barrier or other type of coating inspection techniques anddevices can also, or, be used. For example, fluorescence measurementscan be used to characterize the treatment/coating on the device. Usingthe same apparatus described in FIGS. 10 and 6, a light source 132 or170 (or other radiation source) can be selected that can interact withthe polymer material of the wall 86 and/or a dopant in the polymermaterial of the wall 86. Coupled with a detection system, this can beused to characterize a range of properties including defects,thicknesses and other performance factors.

VI.A. Yet another example of inspection is to use x-rays to characterizethe treatment/coating and/or the polymer itself. In FIG. 10 or 6, thelight source can be replaced with an x-radiation source and the externaldetector can be of a type to measure the x-ray intensity. Elementalanalysis of the barrier or other type of coating can be carried outusing this technique.

VI.A. After molding a device 80, as at the station 22, several potentialissues can arise that will render any subsequent treatment or coatingimperfect, and possibly ineffective. If the devices are inspected priorto coating for these issues, the devices can be coated with a highlyoptimized, optionally up to 6-sigma controlled process that will ensurea desired result (or results).

VI.A. Some of the potential problems that can interfere with treatmentand coating include (depending on the nature of the coated article to beproduced):

VI.A. 1. Large density of particulate contamination defects (forexample, each more than 10 micrometers in its longest dimension), or asmaller density of large particulate contamination (for example, eachmore than 10 micrometers in its longest dimension).

VI.A. 2. Chemical or other surface contamination (for example siliconemold release or oil).

VI.A. 3. High surface roughness, characterized by either a high/largenumber of sharp peaks and/or valleys. This can also be characterized byquantifying the average roughness (Ra) which should be less than 100 nm.

VI.A. 4. Any defect in the device such as a hole that will not allow avacuum to be created.

VI.A. 5. Any defect on the surface of the device that will be used tocreate a seal (for example the open end of a sample collection tube).

VI.A. 6. Large wall thickness non-uniformities which can impede ormodify power coupling through the thickness during treatment or coating.

VI.A. 7. Other defects that will render the barrier or other type ofcoating ineffective.

VI.A. To assure that the treatment/coating operation is successful usingthe parameters in the treatment/coating operation, the device can bepre-inspected for one or more of the above potential issues or otherissues. Previously, an apparatus was disclosed for holding a device (apuck or vessel holder such as 38-68) and moving it through a productionprocess, including various tests and a treatment/coating operation.Several possible tests can be implemented to ensure that a device willhave the appropriate surface for treatment/coating. These include:

VI.A. 1. Optical Inspection, for example, transmission of radiationthrough the device, reflection of radiation from the inside of thedevice or from the outside, absorption of radiation by the device, orinterference with radiation by the device.

VI.A. 2. Digital Inspection—for example, using a digital camera that canmeasure specific lengths and geometries (for example how “round” orotherwise evenly or correctly shaped the open end of a sample collectiontube is relative to a reference).

VI.A. 3. Vacuum leak checking or pressure testing.

VI.A. 4. Sonic (ultrasonic) testing of the device.

VI.A. 5. X-ray analysis.

VI.A. 6. Electrical conductivity of the device (the plastic tubematerial and SiO_(x) have different electrical resistance—on the orderof 1020 Ohm-cm for quartz as a bulk material and on the order of 1014Ohm-cm for polyethylene terephthalate, for example).

VI.A. 7. Thermal conductivity of the device (for example, the thermalconductivity of quartz as a bulk material is about 1.3 W-.degree. K/m,while the thermal conductivity of polyethylene terephthalate is 0.24W-.degree. K/m).

VI.A. 8. Outgassing of the vessel wall, which optionally can be measuredas described below under post-coating inspection to determine anoutgassing baseline.

VI.A. The above testing can be conducted in a station 24 as shown inFIG. 6. In this figure the device (for example a sample collection tube80) can be held in place and a light source (or other source) 132 can beinserted into the device and an appropriate detector 134 positionedoutside of the device to measure the desired result.

VI.A. In the case of vacuum leak detection, the vessel holder and devicecan be coupled to a vacuum pump and a measuring device inserted into thetube. The testing can also be conducted as detailed elsewhere in thespecification.

VI.A. The processing station or device 24 can be a visual inspectionstation, and can be configured to inspect one or more of the interiorsurface 88 of a vessel, its exterior surface 118, or the interior of itsvessel wall 86 between its surfaces 88 and 118 for defects. Theinspection of the exterior surface 118, the interior surface 88, or thevessel wall 86 can be carried out from outside the vessel 80,particularly if the vessel is transparent or translucent to the type ofradiation and wavelength used for inspection. The inspection of theinterior surface 88 can or be facilitated, if desired, by providing anoptical fiber probe inserted into the vessel 80 via the vessel port 92,so a view of the inside of the vessel 80 can be obtained from outsidethe vessel 80. An endoscope or borescope can be used in thisenvironment, for example.

VI.A. Another expedient illustrated in FIG. 6 can be to insert a lightsource 132 within a vessel 80. The light transmitted through the vesselwall 86, and artifacts of the vessel 80 made apparent by the light, canbe detected from outside the vessel 80, as by using a detector measuringapparatus 134. This station or device 24 can be used, for example, todetect and correct or remove misaligned vessels 80 not properly seatedon the vessel port 96 or vessels 80 that have a visible distortion,impurity, or other defect in the wall 86. Visual inspection of thevessel 80 also can be conducted by a worker viewing the vessel 80,instead or in addition to machine inspection.

VI.A. The processing station or device 26, shown in more detail in FIG.7, can be optionally configured to inspect the interior surface 88 of avessel 80 for defects, and for example to measure the gas pressure lossthrough the vessel wall 86, which can be done before a barrier or othertype of coating is provided. This test can be carried out by creating apressure difference between the two sides of the barrier layer 90, as bypressurizing or evacuating the interior of the vessel 80, isolating theinterior 154 of the vessel 80 so the pressure will remain constantabsent leakage around the seal or permeation of gas through the vesselwall, and measuring the pressure change per unit time accumulating fromthese problems. This measurement will not only reveal any gas comingthrough the vessel wall 86, but will also detect a leaking seal betweenthe mouth 82 of the vessel and the O-ring or other seal 100, which mightindicate either a problem with the alignment of the vessel 80 or withthe function of the seal 100. In either case, the tube mis-seating canbe corrected or the tube taken out of the processing line, saving timein attempting to achieve or maintain the proper processing vacuum leveland preventing the dilution of the process gases by air drawn through amalfunctioning seal.

VI.A. The above systems can be integrated into a manufacturing andinspection method comprising multiple steps.

VI.A. FIG. 1 as previously described shows a schematic layout of onepossible method (although this invention is not limited to a singleconcept or approach). First the vessel 80 is visually inspected at thestation or by the device 24, which can include dimensional measurementof the vessel 80. If there are any defects found, the device or vessel80 is rejected and the puck or vessel holder such as 38 is inspected fordefects, recycled or removed.

VI.A. Next the leak rate or other characteristics of the assembly of avessel holder 38 and seated vessel 80 is tested, as at the station 26,and stored for comparison after coating. The puck or vessel holder 38then moves, for example, into the coating step 28. The device or vessel80 is coated with a SiO_(x) or other barrier or other type of coating ata power supply frequency of, for example, 13.56 MHz. Once coated, thevessel holder is retested for its leak rate or other characteristics(this can be carried out as a second test at the testing station 26 or aduplicate or similar station such as 30—the use of a duplicate stationcan increase the system throughput).

VI.A. The coated measurement can be compared to the uncoatedmeasurement. If the ratio of these values exceeds a pre-set requiredlevel, indicating an acceptable overall coating performance, the vesselholder and device move on. An optical testing station 32, for example,follows with a blue light source and an external integrating spheredetector to measure the total light transmitted through the tube. Thevalue can be required to exceed a pre-set limit at which the device isrejected or recycled for additional coating. Next (for devices that arenot rejected), a second optical testing station 34 can be used. In thiscase a point light source can be inserted inside of the tube or vessel80 and pulled out slowly while measurements are taken with a tubular CCDdetector array outside of the tube. The data is then computationallyanalyzed to determine the defect density distribution. Based on themeasurements the device is either approved for final packaging orrejected.

VI.A. The above data optionally can be logged and plotted (for example,electronically) using statistical process control techniques to ensureup to 6-sigma quality.

VI.B. Vessel Inspection by Detecting Outgassing of Container WallThrough Barrier Layer

VI.B. Another embodiment is a method for inspecting a barrier or othertype of layer on a material that outgasses a vapor, having severalsteps. A sample of base material that has at least a partial barrierlayer is provided. Optionally, the pressure is changed in the gas spaceadjacent to the coated surface. In another option, the outgassed gas canbe allowed to diffuse without providing a pressure difference. Theoutgassed gas is measured.

VI.B. In addition a measurement of the efficacy of the interior coating(applied above) can be made by measuring the diffusion rate of aspecific species or adsorbed materials in the wall of the device (priorto coating). When compared to an uncoated (untreated) tube, this type ofmeasurement can provide a direct measurement of the barrier or othertype of properties of the coating or treatment, or the presence orabsence of the coating or treatment. The coating or treatment detected,in addition to or instead of being a barrier layer, can be a lubricitylayer, a hydrophobic layer, a decorative coating, or other types oflayers that modify the outgassing of the substrate, either by increasingor decreasing it.

VI.B. As a specific example using the vessel holder from FIG. 2 andreferring again to FIG. 7, a device or vessel 80 can be inserted intothe puck or vessel holder 44 (the test can also be carried out on aseated vessel 80 carried in a puck or vessel holder such as 44 movingfrom another operation such as coating/treatment). Once the vesselholder moves into the barrier testing area, the measurement tube orprobe 108 can be inserted into the inside (in a similar manner as thegas tube for coating, although the measurement tube does not need toextend as far into the tube). Valves 136 and 148 can both be opened andthe interior of the tube can be evacuated (a vacuum created).

VI.B. Once a desired measurement pressure is reached, the valves 136 and148 can be closed and the pressure gauge 152 can begin measuring thepressure. By measuring the time that a particular pressure (higher thanthe starting pressure) is reached or by measuring the pressure reachedafter a given amount of time, the rate of rise (or leak-rate) of thetube, vessel holder, pump channel and all other parts connected to theinterior volume but isolated by valve 1 and 2 can be measured. If thisvalue is then compared to an uncoated tube, the ratio of the twomeasurements (the coated tube value divided by the uncoated tube value)can yield a measurement of the leak rate through the barrier layer ofthe tube. This measurement technique can require the minimization of theinterior volume of the vessel holder, pump channel and all other partsconnected to the interior volume but isolated by valve 1 and 2 (exceptthe tube/device) to minimize the impact of gas permeation or outgassingfrom these surfaces.

VI.B. Distinctions are made in this disclosure among “permeation,”“leakage,” and “surface diffusion” or “outgassing.”

“Permeation” as used here in reference to a vessel is traverse of amaterial through a wall 346 or other obstruction, as from the outside ofthe vessel to the inside or vice versa along the path 350 in FIG. 29 orthe reverse of that path.

Outgassing refers to the movement of an absorbed or adsorbed materialsuch as the gas molecule 354 or 357 or 359 outward from within the wall346 or coating 348 in FIG. 29, for example through the coating 348 (ifpresent) and into the vessel 358 (to the right in FIG. 29). Outgassingcan also refer to movement of a material such as 354 or 357 out of thewall 346, to the left as shown in FIG. 29, thus to the outside of thevessel 357 as illustrated. Outgassing can also refer to the removal ofadsorbed material from the surface of an article, for example the gasmolecule 355 from the exposed surface of the barrier layer 90.

Leakage refers to the movement of a material around the obstructionrepresented by the wall 346 and coating 348 rather than through or offthe surface of the obstruction, as by passing between a closure and thewall of a vessel closed with a closure.

VI.B. Permeation is indicative of the rate of gas movement through amaterial, devoid of gaps/defects and not relating to leaks oroutgassing. Referring to FIG. 29, which shows a vessel wall or othersubstrate 346 having a barrier layer 348, permeation is traverse of agas entirely through the substrate 346 and coating 348 along the path350 through both layers. Permeation is regarded as a thermodynamic, thusrelatively slow, process.

VI.B. Permeation measurements are very slow, as the permeating gas mustpast entirely through an unbroken wall of the plastic article. In thecase of evacuated blood collection tubes, a measurement of permeation ofgas through its wall is conventionally used as a direct indication ofthe propensity of the vessel to lose vacuum over time, but commonly isan extremely slow measurement, commonly requiring a test duration of sixdays, thus not fast enough to support on-line coating inspection. Suchtesting is ordinarily used for off-line testing of a sample of vessels.

VI.B. Permeation testing also is not a very sensitive measurement of thebarrier efficacy of a thin coating on a thick substrate. Since all thegas flow is through both the coating and the substrate, variations inflow through the thick substrate will introduce variation that is notdue to the barrier efficacy of the coating per se.

VI.B. The inventors have found a much quicker and potentially moresensitive way of measuring the barrier properties of a coating—measuringoutgassing of quickly-separated air or other gaseous or volatileconstituents in the vessel wall through the coating. The gaseous orvolatile constituents can be any material that in fact outgasses, or canbe selected from one or more specific materials to be detected. Theconstituents can include, but are not limited to, oxygen, nitrogen, air,carbon dioxide, water vapor, helium, volatile organic materials such asalcohols, ketones, hydrocarbons, coating precursors, substratecomponents, by-products of the preparation of the coating such asvolatile organosilicons, by-products of the preparation of the coatedsubstrate, other constituents that happen to be present or areintroduced by spiking the substrate, or mixtures or combinations of anyof these.

Surface diffusion and outgassing are synonyms. Each term refers to fluidinitially adsorbed on or absorbed in a wall 346, such as the wall of avessel, and caused to pass into the adjacent space by some motivatingforce, such as drawing a vacuum (creating air movement indicated by thearrow 352 of FIG. 29) within a vessel having a wall to force fluid outof the wall into the interior of the vessel. Outgassing or diffusion isregarded as a kinetic, relatively quick process. It is contemplatedthat, for a wall 346 having substantial resistance to permeation alongthe path 350, outgassing will quickly dislodge the molecules such as 354that are closest to the interface 356 between the wall 346 and thebarrier layer 348. This differential outgassing is suggested by thelarge number of molecules such as 354 near the interface 356 shown asoutgassing, and by the large number of other molecules such as 358 thatare further from the interface 356 and are not shown as outgassing.

VI.B. Accordingly, yet another method is contemplated for inspecting abarrier layer on a material that outgasses a vapor, including severalsteps. A sample of material is provided that outgasses a gas and has atleast a partial barrier layer. The pressure is changed in the gas spaceadjacent to the barrier layer, such that at least some of the materialthat outgasses initially is on the higher-pressure side of the barrierlayer. The outgassed gas transported to the lower-pressure side of thebarrier layer during a test is measured to determine such information aswhether the barrier is present or how effective it is as a barrier.

VI.B. In this method, the material that outgasses a gas can include apolymeric compound, a thermoplastic compound, or one or more compoundshaving both properties. The material that outgasses a gas can includepolyester, for example polyethylene terephthalate. The material thatoutgasses a gas can include a polyolefin, for two examplespolypropylene, a cyclic olefin copolymer, or a combination of these. Thematerial that outgasses a gas can be a composite of two differentmaterials, at least one of which outgasses a vapor. One example is a twolayer structure of polypropylene and polyethylene terephthalate. Anotherexample is a two layer structure of cyclic olefin copolymer andpolyethylene terephthalate. These materials and composites areexemplary; any suitable material or combination of materials can beused.

VI.B. Optionally, the material that outgasses a gas is provided in theform of a vessel having a wall having an outer surface and an innersurface, the inner surface enclosing a lumen. In this embodiment, thebarrier layer optionally is disposed on the vessel wall, optionally onthe inner surface of the vessel wall. The barrier layer could or also bedisposed on the outer surface of the vessel wall. Optionally, thematerial that outgasses a gas can be provided in the form of a film.

VI.B. The barrier layer can be a full or partial coating of any of thepresently described barrier layers. The barrier layer can be less than500 nm thick, or less than 300 nm thick, or less than 100 nm thick, orless than 80 nm thick, or less than 60 nm thick, or less than 50 nmthick, or less than 40 nm thick, or less than 30 nm thick, or less than20 nm thick, or less than 10 nm thick, or less than 5 nm thick.

VI.B. In the case of a coated wall, the inventors have found thatdiffusion/outgassing can be used to determine the coating integrity.Optionally, the pressure is changed in the gas space adjacent to thebarrier layer by at least partially evacuating the lumen or interiorspace of the vessel. This can be done, for example, by connecting thelumen via a duct to a vacuum source to at least partially evacuate thelumen. For example, an uncoated PET wall 346 of a vessel that has beenexposed to ambient air will outgas from its interior surface a certainnumber of oxygen and other gas molecules such as 354 for some time aftera vacuum is drawn. If the same PET wall is coated on the interior with abarrier layer 348, the barrier layer will stop, slow down, or reducethis outgassing. This is true for example of an SiO_(x) barrier layer348, which outgasses less than a plastic surface. By measuring thisdifferential of outgassing between coated and uncoated PET walls, thebarrier effect of the coating 348 for the outgassed material can berapidly determined.

VI.B. If the barrier layer 348 is imperfect, due to holes, cracks, gapsor areas of insufficient thickness or density or composition, the PETwall will outgas preferentially through the imperfections, thusincreasing the total amount of outgassing. The primary source of thecollected gas is from the dissolved gas or vaporizable constituents inthe (sub)surface of the plastic article next to the coating, not fromoutside the article. The amount of outgassing beyond a basic level (forexample the amount passed or released by a standard coating with noimperfections, or the least attainable degree of imperfection, or anaverage and acceptable degree of imperfection) can be measured invarious ways to determine the integrity of the coating.

VI.B. The measurement can be carried out, for example, by providing anoutgassing measurement cell communicating between the lumen and thevacuum source.

VI.B. The measurement cell can implement any of a variety of differentmeasurement technologies. One example of a suitable measurementtechnology is micro-flow technology. For example, the mass flow rate ofoutgassed material can be measured. The measurement can be carried outin a molecular flow mode of operation. An exemplary measurement is adetermination of the volume of gas outgassed through the barrier layerper interval of time.

VI.B. The outgassed gas on the lower-pressure side of the barrier layercan be measured under conditions effective to distinguish the presenceor absence of the barrier layer. Optionally, the conditions effective todistinguish the presence or absence of the barrier layer include a testduration of less than one minute, or less than 50 seconds, or less than40 seconds, or less than 30 seconds, or less than 20 seconds, or lessthan 15 seconds, or less than 10 seconds, or less than 8 seconds, orless than 6 seconds, or less than 4 seconds, or less than 3 seconds, orless than 2 seconds, or less than 1 second.

VI.B. Optionally, the measurement of the presence or absence of thebarrier layer can be confirmed to at least a six-sigma level ofcertainty within any of the time intervals identified above.

VI.B. Optionally, the outgassed gas on the lower-pressure side of thebarrier layer is measured under conditions effective to determine thebarrier improvement factor (BIF) of the barrier layer, compared to thesame material without a barrier layer. A BIF can be determined, forexample, by providing two groups of identical containers, adding abarrier layer to one group of containers, testing a barrier property(such as the rate of outgassing in micrograms per minute or anothersuitable measure) on containers having a barrier, doing the same test oncontainers lacking a barrier, and taking a ratio of the properties ofthe materials with versus without a barrier. For example, if the rate ofoutgassing through the barrier is one-third the rate of outgassingwithout a barrier, the barrier has a BIF of 3.

VI.B. Optionally, outgassing of a plurality of different gases can bemeasured, in instances where more than one type of gas is present, suchas both nitrogen and oxygen in the case of outgassed air. Optionally,outgassing of substantially all or all of the outgassed gases can bemeasured. Optionally, outgassing of substantially all of the outgassedgases can be measured simultaneously, as by using a physical measurementlike the combined mass flow rate of all gases.

VI.B. Measuring the number or partial pressure of individual gas species(such as oxygen or helium) outgassed from the sample can be done morequickly than barometric testing, but the rate of testing is reduced tothe extent that only a fraction of the outgassing is of the measuredspecies. For example, if nitrogen and oxygen are outgassed from the PETwall in the approximately 4:1 proportion of the atmosphere, but onlyoxygen outgassing is measured, the test would need to be run five timesas long as an equally sensitive test (in terms of number of moleculesdetected to obtain results of sufficient statistical quality) thatmeasures all the species outgassed from the vessel wall.

VI.B. For a given level of sensitivity, it is contemplated that a methodthat accounts for the volume of all species outgassed from the surfacewill provide the desired level of confidence more quickly than a testthat measures outgassing of a specific species, such as oxygen atoms.Consequently, outgassing data having practical utility for in-linemeasurements can be generated. Such in-line measurements can optionallybe carried out on every vessel manufactured, thus reducing the number ofidiosyncratic or isolated defects and potentially eliminating them (atleast at the time of measurement).

VI.B. In a practical measurement, a factor changing the apparent amountof outgassing is leakage past an imperfect seal, such as the seal of thevessel seated on a vacuum receptacle as the vacuum is drawn in theoutgassing test. Leakage means a fluid bypassing a solid wall of thearticle, for example fluid passing between a blood tube and its closure,between a syringe plunger and syringe barrel, between a container andits cap, or between a vessel mouth and a seal upon which the vesselmouth is seated (due to an imperfect or mis-seated seal). The word“leakage” is usually indicative of the movement of gas/gas through anopening in the plastic article.

VI.B. Leakage and (if necessary in a given situation) permeation can befactored into the basic level of outgassing, so an acceptable testresult assures both that the vessel is adequately seated on the vacuumreceptacle (thus its seated surfaces are intact and properly formed andpositioned), the vessel wall does not support an unacceptable level ofpermeation (thus the vessel wall is intact and prope SiO_(x) rlyformed), and the coating has sufficient barrier integrity.

VI.B. Outgassing can be measured in various ways, as by barometricmeasurement (measuring the pressure change within the vessel in a givenamount of time after the initial vacuum is drawn) or by measuring thepartial pressure or flow rate of gas outgassed from the sample.Equipment is available that measures a mass flow rate in a molecularflow mode of operation. An example of commercially available equipmentof this type employing Micro-Flow Technology is available from ATC,Inc., Indianapolis, Ind. See U.S. Pat. Nos. 5,861,546, 6,308,556,6,584,828 and EP1356260, which are incorporated by reference here, for afurther description of this known equipment. See also Example 8 in thisspecification, showing an example of outgassing measurement todistinguish barrier coated polyethylene terephthalate (PET) tubes fromuncoated tubes very rapidly and reliably.

VI.B. For a vessel made of polyethylene terephthalate (PET), themicroflow rate is much different for a vessel including an SiO_(x)barrier layer versus a vessel lacking a barrier layer. For example, inWorking Example 8 in this specification, the microflow rate for PET was8 or more micrograms after the test had run for 30 seconds, as shown inFIG. 31. This rate for uncoated PET was much higher than the measuredrate for SiO_(x)-coated PET, which was less than 6 micrograms after thetest had run for 30 sec, again as shown in FIG. 31.

VI.B. One possible explanation for this difference in flow rate is thatuncoated PET contains roughly 0.7 percent equilibrium moisture; thishigh moisture content is believed to cause the observed high microflowrate. With an SiO_(x)-coated PET plastic, the SiO_(x) coating can have ahigher level of surface moisture than an uncoated PET surface. Under thetesting conditions, however, the barrier layer is believed to preventadditional desorption of moisture from the bulk PET plastic, resultingin a lower microflow rate. The microflow rates of oxygen or nitrogenfrom the uncoated PET plastic versus the SiO_(x) coated PET would alsobe expected to be distinguishable.

VI.B. Modifications of the above test for a PET tube might beappropriate when using other materials. For example, polyolefin plasticstend to have little moisture content. An example of a polyolefin havinglow moisture content is TOPAS® cyclic olefin copolymer (COC), having anequilibrium moisture content (0.01 percent) and moisture permeation ratemuch lower than for PET. In the case of COC, uncoated COC plastic canhave microflow rate similar to, or even less than, SiO_(x)-coated COCplastic. This is most likely due to the higher surface moisture contentof the SiO_(x)-coating and the lower equilibrium bulk moisture contentand lower permeation rate of an uncoated COC plastic surface. This makesdifferentiation of uncoated and coated COC articles more difficult.

The present invention shows that exposure of the to-be-tested surfacesof COC articles to moisture (uncoated and coated) results in improvedand consistent microflow separation between uncoated and SiO_(x)-coatedCOC plastics. This is shown in Example 18 in this specification and FIG.57. The moisture exposure can be simply exposure to relative humidityranging from 35%-100%, either in a controlled relative humidity room ordirect exposure to a warm (humidifier) or cold (vaporizer) moisturesource, with the latter preferred.

VI.B. While the validity and scope of the invention are not limitedaccording to the accuracy of this theory, it appears the moisture dopingor spiking of the uncoated COC plastic increases its moisture or otheroutgassable content relative to the already saturated SiO_(x)-coated COCsurface. This can also be accomplished by exposing the coated anduncoated tubes to other gases including oxygen, nitrogen, or theirmixtures, for example air.

VI.B Thus, before measuring the outgassed gas, the barrier layer can becontacted with water, for example water vapor. Water vapor can beprovided, for example, by contacting the barrier layer with air at arelative humidity of 35% to 100%, alternatively 40% to 100%,alternatively 40% to 50%. Instead of or in addition to water, thebarrier layer can be contacted with oxygen, nitrogen or a mixture ofoxygen and nitrogen, for example ambient air. The contacting time can befrom 10 seconds to one hour, alternatively from one minute to thirtyminutes, alternatively from 5 minutes to 25 minutes, alternatively from10 minutes to 20 minutes.

Alternatively, the wall 346 which will be outgassing can be spiked orsupplemented from the side opposite a barrier layer 348, for example byexposing the left side of the wall 346 as shown in FIG. 11 to a materialthat will ingas into the wall 346, then outgas either to the left or tothe right as shown in FIG. 29. Spiking a wall or other material such as346 from the left by ingassing, then measuring outgassing of the spikedmaterial from the right (or vice versa) is distinguished from permeationmeasurement because the material spiked is within the wall 346 at thetime outgassing is measured, as opposed to material that travels thefull path 350 through the wall at the time gas presented through thecoating is being measured. The ingassing can take place over a longperiod of time, as one embodiment before the coating 348 is applied, andas another embodiment after the coating 348 is applied and before it istested for outgassing.

VI.B. Another potential method to increase separation of microflowresponse between uncoated and SiO_(x)-coated plastics is to modify themeasurement pressure and/or temperature. Increasing the pressure ordecreasing the temperature when measuring outgassing can result ingreater relative binding of water molecules in SiO_(x)-coated COC thanin uncoated COC. Thus, the outgassed gas can be measured at a pressurefrom 0.1 Torr to 100 Torr, alternatively from 0.2 Torr to 50 Torr,alternatively from 0.5 Torr to 40 Torr, alternatively from 1 Torr to 30Torr, alternatively from 5 Torr to 100 Torr, alternatively from 10 Torrto 80 Torr, alternatively from 15 Torr to 50 Torr. The outgassed gas canbe measured at a temperature from 0.degree. C. to 50.degree. C.,alternatively from 0.degree. C. to 21.degree. C., alternatively from5.degree. C. to 20.degree. C.

VI.B. Another way contemplated for measuring outgassing, in anyembodiment of the present disclosure, is to employ a microcantilevermeasurement technique. Such a technique is contemplated to allowmeasurement of smaller mass differences in outgassing, potentially onthe order of 10⁻¹² g. (picograms) to 10⁻¹⁵ g. (femtograms). This smallermass detection permits differentiation of coated versus uncoatedsurfaces as well as different coatings in less than a second, optionallyless than 0.1 sec., optionally a matter of microseconds.

VI.B. Microcantilever (MCL) sensors in some instances can respond to thepresence of an outgassed or otherwise provided material by bending orotherwise moving or changing shape due to the absorption of molecules.Microcantilever (MCL) sensors in some instances can respond by shiftingin resonance frequency. In other instances, the MCL sensors can changein both these ways or in other ways. They can be operated in differentenvironments such as gaseous environment, liquids, or vacuum. In gas,microcantilever sensors can be operated as an artificial nose, wherebythe bending pattern of a microfabricated array of eight polymer-coatedsilicon cantilevers is characteristic of the different vapors fromsolvents, flavors, and beverages. The use of any other type ofelectronic nose, operated by any technology, is also contemplated.

Several MCL electronic designs, including piezoresistive, piezoelectric,and capacitive approaches, have been applied and are contemplated tomeasure the movement, change of shape, or frequency change of the MCLsupon exposure to chemicals.

VI.B. One specific example of measuring outgassing can be carried out asfollows. At least one microcantilever is provided that has the property,when in the presence of an outgassed material, of moving or changing toa different shape. The microcantilever is exposed to the outgassedmaterial under conditions effective to cause the microcantilever to moveor change to a different shape. The movement or different shape is thendetected.

VI.B. As one example, the movement or different shape can be detected byreflecting an energetic incident beam from a portion of themicrocantilever that moves or changes shape, before and after exposingthe microcantilever to outgassing, and measuring the resultingdeflection of the reflected beam at a point spaced from the cantilever.The shape is optionally measured at a point spaced from the cantileverbecause the amount of deflection of the beam under given conditions isproportional to the distance of the point of measurement from the pointof reflection of the beam.

VI.B. Several suitable examples of an energetic incident beam are a beamof photons, a beam of electrons, or a combination of two or more ofthese. Alternatively, two or more different beams can be reflected fromthe MCL along different incident and/or reflected paths, to determinemovement or shape change from more than one perspective. Onespecifically contemplated type of energetic incident beam is a beam ofcoherent photons, such as a laser beam. “Photons” as discussed in thisspecification are inclusively defined to include wave energy as well asparticle or photon energy per se.

VI.B. An alternative example of measurement takes advantage of theproperty of certain MCLs of changing in resonant frequency whenencountering an environmental material in an effective amount toaccomplish a change in resonant frequency. This type of measurement canbe carried out as follows. At least one microcantilever is provided thatresonates at a different frequency when in the presence of an outgassedmaterial. The microcantilever can be exposed to the outgassed materialunder conditions effective to cause the microcantilever to resonate at adifferent frequency. The different resonant frequency is then detectedby any suitable means.

VI.B. As one example, the different resonant frequency can be detectedby inputting energy to the microcantilever to induce it to resonatebefore and after exposing the microcantilever to outgassing. Thedifferences between the resonant frequencies of the MCL before and afterexposure to outgassing are determined. Alternatively, instead ofdetermining the difference in resonant frequency, an MCL can be providedthat is known to have a certain resonant frequency when in the presenceof a sufficient concentration or quantity of an outgassed material. Thedifferent resonant frequency or the resonant frequency signaling thepresence of a sufficient quantity of the outgassed material is detectedusing a harmonic vibration sensor.

As one example of using MCL technology for measuring outgassing, an MCLdevice can be incorporated into a quartz vacuum tube linked to a vesseland vacuum pump. A harmonic vibration sensor using a commerciallyavailable piezoresistive cantilever, Wheatstone bridge circuits, apositive feedback controller, an exciting piezoactuator and aphase-locked loop (PLL) demodulator can be constructed. See, e.g.,

-   Hayato Sone, Yoshinori Fujinuma and Sumio Hosaka Picogram Mass    Sensor Using Resonance Frequency Shift of Cantilever, Jpn. J. Appl.    Phys. 43 (2004) 3648;-   Hayato Sone, Ayumi Ikeuchi, Takashi Izumi, Haruki Okano and Sumio    Hosaka Femtogram Mass Biosensor Using Self-Sensing Cantilever for    Allergy Check, Jpn. J. Appl. Phys. 43 (2006) 2301).    To prepare the MCL for detection, one side of the microcantilever    can be coated with gelatin. See, e.g., Hans Peter Lang, Christoph    Gerber, STM and AFM Studies on (Bio)molecular Systems: Unraveling    the Nanoworld, Topics in Current Chemistry, Volume 285/2008. Water    vapor desorbing from the evacuated coated vessel surface binds with    the gelatin, causing the cantilever to bend and its resonant    frequency to change, as measured by laser deflection from a surface    of the cantilever. The change in mass of an uncoated vs. coated    vessel is contemplated to be resolvable in fractions of seconds and    be highly reproducible. The articles cited above in connection with    cantilever technology are incorporated here by reference for their    disclosures of specific MCLs and equipment arrangements that can be    used for detecting and quantifying outgassed species.

Alternative coatings for moisture detection (phosphoric acid) or oxygendetection can be applied to MCLs in place of or in addition to thegelatin coating described above.

VI.B. It is further contemplated that any of the presently contemplatedoutgassing test set-ups can be combined with an SiO_(x) coating station.In such an arrangement, the measurement cell 362 could be as illustratedabove, using the main vacuum channel for PECVD as the bypass 386. In anembodiment, the measurement cell generally indicated as 362 of FIG. 30can be incorporated in a vessel holder such as 50 in which the bypasschannel 386 is configured as the main vacuum duct 94 and the measurementcell 362 is a side channel.

VI.B. This combination of the measurement cell 362 with the vesselholder 50 would optionally allow the outgassing measurement to beconducted without breaking the vacuum used for PECVD. Optionally, thevacuum pump for PECVD would be operated for a short, optionallystandardized amount of time to pump out some or all of the residualreactant gases remaining after the coating step (a pump-down of lessthan one Torr, with a further option of admitting a small amount of air,nitrogen, oxygen, or other gas to flush out or dilute the process gasesbefore pumping down). This would expedite the combined processes ofcoating the vessel and testing the coating for presence and barrierlevel.

VI.B. It will be further appreciated by those skilled in the art, afterreview of this specification, that outgassing measurements and all theother described barrier measurement techniques can be used for manypurposes other than or in addition to determining the efficacy of abarrier layer. For one example, the test can be used on uncoated orcoated vessels to determine the degree of outgassing of the vesselwalls. This test can be used, for example, in cases in which an uncoatedpolymer is required to outgas less than a specified amount.

VI.B. For another example, these outgassing measurements and all theother described barrier measurement techniques can be used on barriercoated or uncoated films, either as a static test or as an in-line testto measure variations in outgassing of a film as it traverses themeasurement cell. The test can be used for determining the continuity orbarrier efficacy of other types of coatings, such as aluminum coatingsor EVOH barrier layers or layers of packaging films.

VI.B. These outgassing measurements and all the other described barriermeasurement techniques can be used to determine the efficacy of abarrier layer applied on the side of a vessel wall, film, or the likeopposite the measurement cell, such as a barrier layer applied on theoutside of a vessel wall and interrogated for outgassing to the interiorof the vessel wall. In this instance, the flow differential would be forpermeation through the barrier layer followed by permeation through thesubstrate film or wall. This measurement would be particularly useful ininstances where the substrate film or wall is quite permeable, such as avery thin or porous film or wall.

VI.B. These outgassing measurements and all the other described barriermeasurement techniques can be used to determine the efficacy of abarrier layer which is an interior layer of a vessel wall, film, or thelike, in which case the measurement cell would detect any outgassingthrough the layer adjacent to the measurement cell plus outgassing,through the barrier layer, of the layer or layers more remote from themeasurement cell than the barrier layer.

VI.B. These outgassing measurements and all the other described barriermeasurement techniques can be used to determine the percentage ofcoverage of a pattern of barrier material over a material thatoutgasses, as by determining the degree of outgassing of the partiallybarrier coated material as a proportion of the amount of outgassingexpected if no barrier were present over any part of the material.

VI.B. One test technique that can be used to increase the rate oftesting for outgassing of a vessel, usable with any outgassing testembodiment in the specification, is to reduce the void volume of thevessel, as by inserting a plunger or closure into the vessel to reducethe void volume of the portion of the vessel tested. Decreasing the voidvolume allows the vessel to be pumped down more quickly to a givenvacuum level, thus decreasing the test interval.

VI.B. Many other applications for the presently described outgassingmeasurements and all the other described barrier measurement techniqueswill be evident to the skilled person after reviewing thisspecification.

VII. PECVD Treated Vessels

VII. Vessels are contemplated having a barrier layer 90 (shown in FIG.2, for example), which can be an coating applied to a thickness of atleast 2 nm, or at least 4 nm, or at least 7 nm, or at least 10 nm, or atleast 20 nm, or at least 30 nm, or at least 40 nm, or at least 50 nm, orat least 100 nm, or at least 150 nm, or at least 200 nm, or at least 300nm, or at least 400 nm, or at least 500 nm, or at least 600 nm, or atleast 700 nm, or at least 800 nm, or at least 900 nm. The coating can beup to 1000 nm, or at most 900 nm, or at most 800 nm, or at most 700 nm,or at most 600 nm, or at most 500 nm, or at most 400 nm, or at most 300nm, or at most 200 nm, or at most 100 nm, or at most 90 nm, or at most80 nm, or at most 70 nm, or at most 60 nm, or at most 50 nm, or at most40 nm, or at most 30 nm, or at most 20 nm, or at most 10 nm, or at most5 nm thick. Specific thickness ranges composed of any one of the minimumthicknesses expressed above, plus any equal or greater one of themaximum thicknesses expressed above, are expressly contemplated. Thethickness of the SiO_(x) or other coating can be measured, for example,by transmission electron microscopy (TEM), and its composition can bemeasured by X-ray photoelectron spectroscopy (XPS).

VII. It is contemplated that the choice of the material to be barredfrom permeating the coating and the nature of the SiO_(x) coatingapplied can affect its barrier efficacy. For example, two examples ofmaterial commonly intended to be barred are oxygen and water/watervapor. Materials commonly are a better barrier to one than to the other.This is believed to be so at least in part because oxygen is transmittedthrough the coating by a different mechanism than water is transmitted.

VII. Oxygen transmission is affected by the physical features of thecoating, such as its thickness, the presence of cracks, and otherphysical details of the coating. Water transmission, on the other hand,is believed to commonly be affected by chemical factors, i.e. thematerial of which the coating is made, more than physical factors. Theinventors also believe that at least one of these chemical factors is asubstantial concentration of OH moieties in the coating, which leads toa higher transmission rate of water through the barrier. An SiO_(x)coating often contains OH moieties, and thus a physically sound coatingcontaining a high proportion of OH moieties is a better barrier tooxygen than to water. A physically sound carbon-based barrier, such asamorphous carbon or diamond-like carbon (DLC) commonly is a betterbarrier to water than is aSiO_(x) coating because the carbon-basedbarrier more commonly has a lower concentration of OH moieties.

VII. Other factors lead to a preference for an SiO_(x) coating, however,such as its oxygen barrier efficacy and its close chemical resemblanceto glass and quartz. Glass and quartz (when used as the base material ofa vessel) are two materials long known to present a very high barrier tooxygen and water transmission as well as substantial inertness to manymaterials commonly carried in vessels. Thus, it is commonly desirable tooptimize the water barrier properties such as the water vaportransmission rate (WVTR) of an SiO_(x) coating, rather than choosing adifferent or additional type of coating to serve as a water transmissionbarrier.

VII. Several ways contemplated to improve the WVTR of an SiO_(x) coatingare as follow.

VII. The concentration ratio of organic moieties (carbon and hydrogencompounds) to OH moieties in the deposited coating can be increased.This can be done, for example, by increasing the proportion of oxygen inthe feed gases (as by increasing the oxygen feed rate or by lowering thefeed rate of one or more other constituents). The lowered incidence ofOH moieties is believed to result from increasing the degree of reactionof the oxygen feed with the hydrogen in the silicone source to yieldmore volatile water in the PECVD exhaust and a lower concentration of OHmoieties trapped or incorporated in the coating.

VII. Higher energy can be applied in the PECVD process, either byraising the plasma generation power level, by applying the power for alonger period, or both. An increase in the applied energy must beemployed with care when used to coat a plastic tube or other device, asit also has a tendency to distort the vessel being treated, to theextent the tube absorbs the plasma generation power. This is why RFpower is contemplated in the context of present application. Distortionof the medical devices can be reduced or eliminated by employing theenergy in a series of two or more pulses separated by cooling time, bycooling the vessels while applying energy, by applying the coating in ashorter time (commonly thus making it thinner), by selecting a frequencyof the applied coating that is absorbed minimally by the base materialselected for being coated, and/or by applying more than one coating,with time in between the respective energy application steps. Forexample, high power pulsing can be used with a duty cycle of 1millisecond on, 99 milliseconds off, while continuing to feed theprocess gas. The process gas is then the coolant, as it keeps flowingbetween pulses. Another alternative is to reconfigure the powerapplicator, as by adding magnets to confine the plasma increase theeffective power application (the power that actually results inincremental coating, as opposed to waste power that results in heatingor unwanted coating). This expedient results in the application of morecoating-formation energy per total Watt-hour of energy applied. See forexample U.S. Pat. No. 5,904,952.

VII. An oxygen post-treatment of the coating can be applied to remove OHmoieties from the previously-deposited coating. This treatment is alsocontemplated to remove residual volatile organosilicon compounds orsilicones or oxidize the coating to form additional SiO_(x).

VII. The plastic base material tube can be preheated.

VII. A different volatile source of silicon, such ashexamethyldisilazane (HMDZ), can be used as part or all of the siliconefeed. It is contemplated that changing the feed gas to HMDZ will addressthe problem because this compound has no oxygen moieties in it, assupplied. It is contemplated that one source of OH moieties in theHMDSO-sourced coating is hydrogenation of at least some of the oxygenatoms present in unreacted HMDSO.

VII. A composite coating can be used, such as a carbon-based coatingcombined with SiO_(x). This can be done, for example, by changing thereaction conditions or by adding a substituted or unsubstitutedhydrocarbon, such as an alkane, alkene, or alkyne, to the feed gas aswell as an organosilicon-based compound. See for example U.S. Pat. No.5,904,952, which states in relevant part: “For example, inclusion of alower hydrocarbon such as propylene provides carbon moieties andimproves most properties of the deposited films (except for lighttransmission), and bonding analysis indicates the film to be silicondioxide in nature. Use of methane, methanol, or acetylene, however,produces films that are silicone in nature. The inclusion of a minoramount of gaseous nitrogen to the gas stream provides nitrogen moietiesin the deposited films and increases the deposition rate, improves thetransmission and reflection optical properties on glass, and varies theindex of refraction in response to varied amounts of N₂. The addition ofnitrous oxide to the gas stream increases the deposition rate andimproves the optical properties, but tends to decrease the filmhardness.”

VII. A diamond-like carbon (DLC) coating can be formed as the primary orsole coating deposited. This can be done, for example, by changing thereaction conditions or by feeding methane, hydrogen, and helium to aPECVD process. These reaction feeds have no oxygen, so no OH moietiescan be formed. For one example, an SiO_(x) coating can be applied on theinterior of a tube or syringe barrel and an outer DLC coating can beapplied on the exterior surface of a tube or syringe barrel. Or, theSiO_(x) and DLC coatings can both be applied as a single layer or plurallayers of an interior tube or syringe barrel coating.

VII. Referring to FIG. 2, the barrier or other type of coating 90reduces the transmission of atmospheric gases into the vessel 80 throughits interior surface 88. Or, the barrier or other type of coating 90reduces the contact of the contents of the vessel 80 with the interiorsurface 88. The barrier or other type of coating can comprise, forexample, SiO_(x), amorphous (for example, diamond-like) carbon, or acombination of these.

VII. Any coating described herein can be used for coating a surface, forexample a plastic surface. It can further be used as a barrier layer,for example as a barrier against a gas or liquid, optionally againstwater vapor, oxygen and/or air. It can also be used for preventing orreducing mechanical and/or chemical effects which the coated surfacewould have on a compound or composition if the surface were uncoated.For example, it can prevent or reduce the precipitation of a compound orcomposition, for example insulin precipitation or blood clotting orplatelet activation.

VII.A. Evacuated Blood Collection Vessels

VII.A.1. Tubes

VII.A.I. Referring to FIG. 2, more details of the vessel such as 80 areshown. The illustrated vessel 80 can be generally tubular, having anopening 82 at one end of the vessel, opposed by a closed end 84. Thevessel 80 also has a wall 86 defining an interior surface 88. Oneexample of the vessel 80 is a medical sample tube, such as an evacuatedblood collection tube, as commonly is used by a phlebotomist forreceiving a venipuncture sample of a patient's blood for use in amedical laboratory.

VII.A.1. The vessel 80 can be made, for example, of thermoplasticmaterial. Some examples of suitable thermoplastic material arepolyethylene terephthalate or a polyolefin such as polypropylene or acyclic polyolefin copolymer.

VII.A.1. The vessel 80 can be made by any suitable method, such as byinjection molding, by blow molding, by machining, by fabrication fromtubing stock, or by other suitable means. PECVD can be used to form acoating on the internal surface of SiO_(x).

VII.A.1. If intended for use as an evacuated blood collection tube, thevessel 80 desirably can be strong enough to withstand a substantiallytotal internal vacuum substantially without deformation when exposed toan external pressure of 760 Torr or atmospheric pressure and othercoating processing conditions. This property can be provided, in athermoplastic vessel 80, by providing a vessel 80 made of suitablematerials having suitable dimensions and a glass transition temperaturehigher than the processing temperature of the coating process, forexample a cylindrical wall 86 having sufficient wall thickness for itsdiameter and material.

VII.A.1. Medical vessels or containers like sample collection tubes andsyringes are relatively small and are injection molded with relativelythick walls, which renders them able to be evacuated without beingcrushed by the ambient atmospheric pressure. They are thus stronger thancarbonated soft drink bottles or other larger or thinner-walled plasticcontainers. Since sample collection tubes designed for use as evacuatedvessels typically are constructed to withstand a full vacuum duringstorage, they can be used as vacuum chambers.

VII.A.1. Such adaptation of the vessels to be their own vacuum chambersmight eliminate the need to place the vessels into a vacuum chamber forPECVD treatment, which typically is carried out at very low pressure.The use of a vessel as its own vacuum chamber can result in fasterprocessing time (since loading and unloading of the parts from aseparate vacuum chamber is not necessary) and can lead to simplifiedequipment configurations. Furthermore, a vessel holder is contemplated,for certain embodiments, that will hold the device (for alignment to gastubes and other apparatus), seal the device (so that the vacuum can becreated by attaching the vessel holder to a vacuum pump) and move thedevice between molding and subsequent processing steps.

VII.A.1. A vessel 80 used as an evacuated blood collection tube shouldbe able to withstand external atmospheric pressure, while internallyevacuated to a reduced pressure useful for the intended application,without a substantial volume of air or other atmospheric gas leakinginto the tube (as by bypassing the closure) or permeating through thewall 86 during its shelf life. If the as-molded vessel 80 cannot meetthis requirement, it can be processed by coating the interior surface 88with a barrier or other type of coating 90. It is desirable to treatand/or coat the interior surfaces of these devices (such as samplecollection tubes and syringe barrels) to impart various properties thatwill offer advantages over existing polymeric devices and/or to mimicexisting glass products. It is also desirable to measure variousproperties of the devices before and/or after treatment or coating.

VII.A.1.a. Coating Deposited from an Organosilicon Precursor Made by InSitu Polymerizing Organosilicon Precursor

VII.A.1.a. A process is contemplated for applying a lubricity layercharacterized as defined in the Definition Section on a substrate, forexample the interior of the barrel of a syringe, comprising applying oneof the described precursors on or in the vicinity of a substrate at athickness of 1 to 5000 nm, optionally 10 to 1000 nm, optionally 10-200nm, optionally 20 to 100 nm thick and crosslinking or polymerizing (orboth) the coating, optionally in a PECVD process, to provide alubricated surface. The coating applied by this process is alsocontemplated to be new.

VII.A.1.a. A coating of Si_(w)O_(x)C_(y)H_(z) as defined in theDefinition Section can have utility as a hydrophobic layer. Coatings ofthis kind are contemplated to be hydrophobic, independent of whetherthey function as lubricity layers. A coating or treatment is defined as“hydrophobic” if it lowers the wetting tension of a surface, compared tothe corresponding uncoated or untreated surface. Hydrophobicity is thusa function of both the untreated substrate and the treatment.

VII.A.1.a. The degree of hydrophobicity of a coating can be varied byvarying its composition, properties, or deposition method. For example,a coating of SiO_(x) having little or no hydrocarbon content is morehydrophilic than a coating of Si_(w)O_(x)C_(y)H_(z) as defined in theDefinition Section. Generally speaking, the higher the C—H_(x) (e.g. CH,CH₂, or CH₃) moiety content of the coating, either by weight, volume, ormolarity, relative to its silicon content, the more hydrophobic thecoating.

VII.A.1.a. A hydrophobic layer can be very thin, having a thickness ofat least 4 nm, or at least 7 nm, or at least 10 nm, or at least 20 nm,or at least 30 nm, or at least 40 nm, or at least 50 nm, or at least 100nm, or at least 150 nm, or at least 200 nm, or at least 300 nm, or atleast 400 nm, or at least 500 nm, or at least 600 nm, or at least 700nm, or at least 800 nm, or at least 900 nm. The coating can be up to1000 nm, or at most 900 nm, or at most 800 nm, or at most 700 nm, or atmost 600 nm, or at most 500 nm, or at most 400 nm, or at most 300 nm, orat most 200 nm, or at most 100 nm, or at most 90 nm, or at most 80 nm,or at most 70 nm, or at most 60 nm, or at most 50 nm, or at most 40 nm,or at most 30 nm, or at most 20 nm, or at most 10 nm, or at most 5 nmthick. Specific thickness ranges composed of any one of the minimumthicknesses expressed above, plus any equal or greater one of themaximum thicknesses expressed above, are expressly contemplated.

VII.A.1.a. One utility for such a hydrophobic layer is to isolate athermoplastic tube wall, made for example of polyethylene terephthalate(PET), from blood collected within the tube. The hydrophobic layer canbe applied on top of a hydrophilic SiO_(x) coating on the internalsurface of the tube. The SiO_(x) coating increases the barrierproperties of the thermoplastic tube and the hydrophobic layer changesthe surface energy of blood contact surface with the tube wall. Thehydrophobic layer can be made by providing a precursor selected fromthose identified in this specification. For example, the hydrophobiclayer precursor can comprise hexamethyldisiloxane (HMDSO) oroctamethylcyclotetrasiloxane (OMCTS).

VII.A.1.a. Another use for a hydrophobic layer is to prepare a glasscell preparation tube. The tube has a wall defining a lumen, ahydrophobic layer in the internal surface of the glass wall, andcontains a citrate reagent. The hydrophobic layer can be made byproviding a precursor selected from those identified elsewhere in thisspecification. For another example, the hydrophobic layer precursor cancomprise hexamethyldisiloxane (HMDSO) or octamethylcyclotetrasiloxane(OMCTS). Another source material for hydrophobic layers is an alkyltrimethoxysilane of the formula:R—Si(OCH₃)₃in which R is a hydrogen atom or an organic substituent, for examplemethyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, vinyl,alkyne, epoxide, or others. Combinations of two or more of these arealso contemplated.

VII.A.1.a. Combinations of acid or base catalysis and heating, using analkyl trimethoxysilane precursor as described above, can condense theprecursor (removing ROH by-products) to form crosslinked polymers, whichcan optionally be further crosslinked via an alternative method. Onespecific example is by Shimojima et. al. J. Mater. Chem., 2007, 17,658-663.

VII.A.1.a. A lubricity layer, characterized as defined in the DefinitionSection, can be applied as a subsequent coating after applying anSiO_(x) barrier layer to the interior surface 88 of the vessel 80 toprovide a lubricity layer, particularly if the lubricity layer is aliquid organosiloxane compound at the end of the coating process.

VII.A.1.a. Optionally, after the lubricity layer is applied, it can bepost-cured after the PECVD process. Radiation curing approaches,including UV-initiated (free radial or cationic), electron-beam(E-beam), and thermal as described in Development Of NovelCycloaliphatic Siloxanes For Thermal And UV-Curable Applications (RubyChakraborty Dissertation, can 2008) be utilized.

VII.A.1.a. Another approach for providing a lubricity layer is to use asilicone demolding agent when injection-molding the thermoplastic vesselto be lubricated. For example, it is contemplated that any of thedemolding agents and latent monomers causing in-situ thermal lubricitylayer formation during the molding process can be used. Or, theaforementioned monomers can be doped into traditional demolding agentsto accomplish the same result.

VII.A.1.a. A lubricity layer, characterized as defined in the DefinitionSection, is particularly contemplated for the internal surface of asyringe barrel as further described below. A lubricated internal surfaceof a syringe barrel can reduce the plunger sliding force needed toadvance a plunger in the barrel during operation of a syringe, or thebreakout force to start a plunger moving after the prefilled syringeplunger has pushed away the intervening lubricant or adhered to thebarrel, for example due to decomposition of the lubricant between theplunger and the barrel. As explained elsewhere in this specification, alubricity layer also can be applied to the interior surface 88 of thevessel 80 to improve adhesion of a subsequent coating of SiO_(x).

VII.A.1.a. Thus, the coating 90 can comprise a layer of SiO_(x) and alubricity layer and/or hydrophobic layer, characterized as defined inthe Definition Section. The lubricity layer and/or hydrophobic layer ofSi_(w)O_(x)C_(y)H_(z) can be deposited between the layer of SiO_(x) andthe interior surface of the vessel. Or, the layer of SiO_(x) can bedeposited between the lubricity layer and/or hydrophobic layer and theinterior surface of the vessel. Or, three or more layers, eitheralternating or graduated between these two coating compositions: (1) alayer of SiO_(x) and (2) the lubricity layer and/or hydrophobic layer;can also be used. The layer of SiO_(x) can be deposited adjacent to thelubricity layer and/or hydrophobic layer or remotely, with at least oneintervening layer of another material. The layer of SiO_(x) can bedeposited adjacent to the interior surface of the vessel. Or, thelubricity layer and/or hydrophobic layer can be deposited adjacent tothe interior surface of the vessel.

VII.A.1.a. Another expedient contemplated here, for adjacent layers ofSiO_(x) and a lubricity layer and/or hydrophobic layer, is a gradedcomposite of Si_(w)O_(x)C_(y)H_(z), as defined in the DefinitionSection. A graded composite can be separate layers of a lubricity layerand/or hydrophobic layer and SiO_(x) with a transition or interface ofintermediate composition between them, or separate layers of a lubricitylayer and/or hydrophobic layer and SiO.sub.x with an intermediatedistinct layer of intermediate composition between them, or a singlelayer that changes continuously or in steps from a composition of alubricity layer and/or hydrophobic layer to a composition more likeSiO_(x), going through the coating in a normal direction.

VII.A.1.a. The grade in the graded composite can go in either direction.For example, the a lubricity layer and/or hydrophobic layer can beapplied directly to the substrate and graduate to a composition furtherfrom the surface of SiO_(x). Or, the composition of SiO_(x) can beapplied directly to the substrate and graduate to a composition furtherfrom the surface of a lubricity layer and/or hydrophobic layer. Agraduated coating is particularly contemplated if a coating of onecomposition is better for adhering to the substrate than the other, inwhich case the better-adhering composition can, for example, be applieddirectly to the substrate. It is contemplated that the more distantportions of the graded coating can be less compatible with the substratethan the adjacent portions of the graded coating, since at any point thecoating is changing gradually in properties, so adjacent portions atnearly the same depth of the coating have nearly identical composition,and more widely physically separated portions at substantially differentdepths can have more diverse properties. It is also contemplated that acoating portion that forms a better barrier against transfer of materialto or from the substrate can be directly against the substrate, toprevent the more remote coating portion that forms a poorer barrier frombeing contaminated with the material intended to be barred or impeded bythe barrier.

VII.A.1.a. The coating, instead of being graded, optionally can havesharp transitions between one layer and the next, without a substantialgradient of composition. Such coatings can be made, for example, byproviding the gases to produce a layer as a steady state flow in anon-plasma state, then energizing the system with a brief plasmadischarge to form a coating on the substrate. If a subsequent coating isto be applied, the gases for the previous coating are cleared out andthe gases for the next coating are applied in a steady-state fashionbefore energizing the plasma and again forming a distinct layer on thesurface of the substrate or its outermost previous coating, with littleif any gradual transition at the interface.

VII.A.1.b. Citrate Blood Tube Having Wall Coated with Hydrophobic LayerDeposited from an Organosilicon Precursor

VII.A.1.b. Another embodiment is a cell preparation tube having a wallprovided with a hydrophobic layer on its inside surface and containingan aqueous sodium citrate reagent. The hydrophobic layer can be also beapplied on top of a hydrophilic SiO_(x) coating on the internal surfaceof the tube. The SiO_(x) coating increases the barrier properties of thethermoplastic tube and the hydrophobic layer changes the surface energyof blood contact surface with the tube wall.

VII.A.1.b. The wall is made of thermoplastic material having an internalsurface defining a lumen.

VII.A.1.b. A blood collection tube according to the embodiment VII.A.1.bcan have a first layer of SiO_(x) on the internal surface of the tube,applied as explained in this specification, to function as an oxygenbarrier and extend the shelf life of an evacuated blood collection tubemade of thermoplastic material. A second layer of a hydrophobic layer,characterized as defined in the Definition Section, can then be appliedover the barrier layer on the internal surface of the tube to provide ahydrophobic surface. The coating is effective to reduce the plateletactivation of blood plasma treated with a sodium citrate additive andexposed to the inner surface, compared to the same type of walluncoated.

VII.A.1.b. PECVD is used to form a hydrophobic layer on the internalsurface, characterized as defined in the Definition Section. Unlikeconventional citrate blood collection tubes, the blood collection tubehaving a hydrophobic layer, characterized as defined in the DefinitionSection does not require a coating of baked on silicone on the vesselwall, as is conventionally applied to make the surface of the tubehydrophobic.

VII.A.1.b. Both layers can be applied using the same precursor, forexample HMDSO or OMCTS, and different PECVD reaction conditions.

VII.A.1.b. A sodium citrate anticoagulation reagent is then placedwithin the tube and it is evacuated and sealed with a closure to producean evacuated blood collection tube. The components and formulation ofthe reagent are known to those skilled in the art. The aqueous sodiumcitrate reagent is disposed in the lumen of the tube in an amounteffective to inhibit coagulation of blood introduced into the tube.

VII.A.1.c. SiO_(x) Barrier Coated Double Wall Plastic Vessel—COC, PET,SiO_(x) Layers

VII.A.1.c. Another embodiment is a vessel having a wall at leastpartially enclosing a lumen. The wall has an interior polymer layerenclosed by an exterior polymer layer. One of the polymer layers is alayer at least 0.1 mm thick of a cyclic olefin copolymer (COC) resindefining a water vapor barrier. Another of the polymer layers is a layerat least 0.1 mm thick of a polyester resin.

VII.A.1.c. The wall includes an oxygen barrier layer of SiO_(x) having athickness of from about 10 to about 500 angstroms.

VII.A.1.c. In an embodiment, illustrated in FIG. 36, the vessel 80 canbe a double-walled vessel having an inner wall 408 and an outer wall410, respectively made of the same or different materials. Oneparticular embodiment of this type can be made with one wall molded froma cyclic olefin copolymer (COC) and the other wall molded from apolyester such as polyethylene terephthalate (PET), with an SiO_(x)coating as previously described on the interior surface 412. As needed,a tie coating or layer can be inserted between the inner and outer wallsto promote adhesion between them. An advantage of this wall constructionis that walls having different properties can be combined to form acomposite having the respective properties of each wall.

VII.A.1.c. As one example, the inner wall 408 can be made of PET coatedon the interior surface 412 with an SiO_(x) barrier layer, and the outerwall 410 can be made of COC. PET coated with SiO_(x), as shown elsewherein this specification, is an excellent oxygen barrier, while COC is anexcellent barrier for water vapor, providing a low water vaportransition rate (WVTR). This composite vessel can have superior barrierproperties for both oxygen and water vapor. This construction iscontemplated, for example, for an evacuated medical sample collectiontube that contains an aqueous reagent as manufactured, and has asubstantial shelf life, so it should have a barrier preventing transferof water vapor outward or transfer of oxygen or other gases inwardthrough its composite wall during its shelf life.

VII.A.1.c. As another example, the inner wall 408 can be made of COCcoated on the interior surface 412 with an SiO_(x) barrier layer, andthe outer wall 410 can be made of PET. This construction iscontemplated, for example, for a prefilled syringe that contains anaqueous sterile fluid as manufactured. The SiO_(x) barrier will preventoxygen from entering the syringe through its wall. The COC inner wallwill prevent ingress or egress of other materials such as water, thuspreventing the water in the aqueous sterile fluid from leachingmaterials from the wall material into the syringe. The COC inner wall isalso contemplated to prevent water derived from the aqueous sterilefluid from passing out of the syringe (thus undesirably concentratingthe aqueous sterile fluid), and will prevent non-sterile water or otherfluids outside the syringe from entering through the syringe wall andcausing the contents to become non-sterile. The COC inner wall is alsocontemplated to be useful for decreasing the breaking force or frictionof the plunger against the inner wall of a syringe.

VII.A.1.d. Method of Making Double Wall Plastic Vessel—COC, PET, SiO_(x)Layers

VII.A.1.d. Another embodiment is a method of making a vessel having awall having an interior polymer layer enclosed by an exterior polymerlayer, one layer made of COC and the other made of polyester. The vesselis made by a process including introducing COC and polyester resinlayers into an injection mold through concentric injection nozzles.

VII.A.1.d. An optional additional step is applying an amorphous carboncoating to the vessel by PECVD, as an inside coating, an outsidecoating, or as an interlayer coating located between the layers.

VII.A.1.d. An optional additional step is applying an SiO_(x) barrierlayer to the inside of the vessel wall, where SiO_(x) is defined asbefore. Another optional additional step is post-treating the SiO_(x)layer with a process gas consisting essentially of oxygen andessentially free of a volatile silicon compound.

VII.A.1.d. Optionally, the SiO_(x) coating can be formed at leastpartially from a silazane feed gas.

VII.A.1.d. The vessel 80 shown in FIG. 36 can be made from the insideout, for one example, by injection molding the inner wall in a firstmold cavity, then removing the core and molded inner wall from the firstmold cavity to a second, larger mold cavity, then injection molding theouter wall against the inner wall in the second mold cavity. Optionally,a tie layer can be provided to the exterior surface of the molded innerwall before over-molding the outer wall onto the tie layer.

VII.A.1.d. Or, the vessel 80 shown in FIG. 36 can be made from theoutside in, for one example, by inserting a first core in the moldcavity, injection molding the outer wall in the mold cavity, thenremoving the first core from the molded first wall and inserting asecond, smaller core, then injection molding the inner wall against theouter wall still residing in the mold cavity. Optionally, a tie layercan be provided to the interior surface of the molded outer wall beforeover-molding the inner wall onto the tie layer.

VII.A.1.d. Or, the vessel 80 shown in FIG. 36 can be made in a two shotmold. This can be done, for one example, by injection molding materialfor the inner wall from an inner nozzle and the material for the outerwall from a concentric outer nozzle. Optionally, a tie layer can beprovided from a third, concentric nozzle disposed between the inner andouter nozzles. The nozzles can feed the respective wall materialssimultaneously. One useful expedient is to begin feeding the outer wallmaterial through the outer nozzle slightly before feeding the inner wallmaterial through the inner nozzle. If there is an intermediateconcentric nozzle, the order of flow can begin with the outer nozzle andcontinue in sequence from the intermediate nozzle and then from theinner nozzle. Or, the order of beginning feeding can start from theinside nozzle and work outward, in reverse order compared to thepreceding description.

VII.A.1.e. Barrier Layer Made of Glass

VII.A.1.e. Another embodiment is a vessel including a barrier layer anda closure. The vessel is generally tubular and made of thermoplasticmaterial. The vessel has a mouth and a lumen bounded at least in part bya wall having an inner surface interfacing with the lumen. There is anat least essentially continuous barrier layer made of glass on the innersurface of the wall. A closure covers the mouth and isolates the lumenof the vessel from ambient air.

VII.A.1.e. The vessel 80 can also be made, for example of glass of anytype used in medical or laboratory applications, such as soda-limeglass, borosilicate glass, or other glass formulations. Other vesselshaving any shape or size, made of any material, are also contemplatedfor use in the system 20. One function of coating a glass vessel can beto reduce the ingress of ions in the glass, either intentionally or asimpurities, for example sodium, calcium, or others, from the glass tothe contents of the vessel, such as a reagent or blood in an evacuatedblood collection tube. Another function of coating a glass vessel inwhole or in part, such as selectively at surfaces contacted in slidingrelation to other parts, is to provide lubricity to the coating, forexample to ease the insertion or removal of a stopper or passage of asliding element such as a piston in a syringe. Still another reason tocoat a glass vessel is to prevent a reagent or intended sample for thevessel, such as blood, from sticking to the wall of the vessel or anincrease in the rate of coagulation of the blood in contact with thewall of the vessel.

VII.A.1.e.i. A related embodiment is a vessel as described in theprevious paragraph, in which the barrier layer is made of soda limeglass, borosilicate glass, or another type of glass.

VII.A.2. Stoppers

VII.A.2. FIGS. 23-25 illustrate a vessel 268, which can be an evacuatedblood collection tube, having a closure 270 to isolate the lumen 274from the ambient environment. The closure 270 comprises ainterior-facing surface 272 exposed to the lumen 274 of the vessel 268and a wall-contacting surface 276 that is in contact with the innersurface 278 of the vessel wall 280. In the illustrated embodiment theclosure 270 is an assembly of a stopper 282 and a shield 284.

VII.A.2.a. Method of Applying Lubricity layer to Stopper in VacuumChamber

VII.A.2.a. Another embodiment is a method of applying a coating on anelastomeric stopper such as 282. The stopper 282, separate from thevessel 268, is placed in a substantially evacuated chamber. A reactionmixture is provided including plasma forming gas, i.e. an organosiliconcompound gas, optionally an oxidizing gas, and optionally a hydrocarbongas. Plasma is formed in the reaction mixture, which is contacted withthe stopper. A lubricity and/or hydrophobic layer, characterized asdefined in the Definition Section, is deposited on at least a portion ofthe stopper.

VII.A.2.a. In the illustrated embodiment, the wall-contacting surface276 of the closure 270 is coated with a lubricity layer 286.

VII.A.2.a. In some embodiments, the lubricity and/or hydrophobic layer,characterized as defined in the Definition Section, is effective toreduce the transmission of one or more constituents of the stopper, suchas a metal ion constituent of the stopper, or of the vessel wall, intothe vessel lumen. Certain elastomeric compositions of the type usefulfor fabricating a stopper 282 contain trace amounts of one or more metalions. These ions sometimes should not be able to migrate into the lumen274 or come in substantial quantities into contact with the vesselcontents, particularly if the sample vessel 268 is to be used to collecta sample for trace metal analysis. It is contemplated for example thatcoatings containing relatively little organic content, i.e. where y andz of Si_(w)O_(x)C_(y)H_(z) as defined in the Definition Section are lowor zero, are particularly useful as a metal ion barrier in thisapplication. Regarding silica as a metal ion barrier see, for example,Anupama Mallikarjunan, Jasbir Juneja, Guangrong Yang, Shyam P. Murarka,and Toh-Ming Lu, The Effect of Interfacial Chemistry on Metal IonPenetration into Polymeric Films, Mat. Res. Soc. Symp. Proc., Vol. 734,pp. B9.60.1 to B9.60.6 (Materials Research Society, 2003); U.S. Pat.Nos. 5,578,103 and 6,200,658, and European Appl. EP0697378 A2, which areall incorporated here by reference. It is contemplated, however, thatsome organic content can be useful to provide a more elastic coating andto adhere the coating to the elastomeric surface of the stopper 282.

VII.A.2.a. In some embodiments, the lubricity and/or hydrophobic layer,characterized as defined in the Definition Section, can be a compositeof material having first and second layers, in which the first or innerlayer 288 interfaces with the elastomeric stopper 282 and is effectiveto reduce the transmission of one or more constituents of the stopper282 into the vessel lumen. The second layer 286 can interface with theinner wall 280 of the vessel and is effective as a lubricity layer toreduce friction between the stopper 282 and the inner wall 280 of thevessel when the stopper 282 is seated on or in the vessel 268. Suchcomposites are described in connection with syringe coatings elsewherein this specification.

VII.A.2.a. Or, the first and second layers 288 and 286 are defined by acoating of graduated properties, in which the values of y and z definedin the Definition Section are greater in the first layer than in thesecond layer.

VII.A.2.a. The lubricity and/or hydrophobic layer can be applied, forexample, by PECVD substantially as previously described. The lubricityand/or hydrophobic layer can be, for example, between 0.5 and 5000 nm (5to 50,000 Angstroms) thick, or between 1 and 5000 nm thick, or between 5and 5000 nm thick, or between 10 and 5000 nm thick, or between 20 and5000 nm thick, or between 50 and 5000 nm thick, or between 100 and 5000nm thick, or between 200 and 5000 nm thick, or between 500 and 5000 nmthick, or between 1000 and 5000 nm thick, or between 2000 and 5000 nmthick, or between 3000 and 5000 nm thick, or between 4000 and 10,000 nmthick.

VII.A.2.a. Certain advantages are contemplated for plasma coatedlubricity layers, versus the much thicker (one micron or greater)conventional spray applied silicone lubricants. Plasma coatings have amuch lower migratory potential to move into blood versus sprayed ormicron-coated silicones, both because the amount of plasma coatedmaterial is much less and because it can be more intimately applied tothe coated surface and better bonded in place.

VII.A.2.a. Nanocoatings, as applied by PECVD, are contemplated to offerlower resistance to sliding of an adjacent surface or flow of anadjacent fluid than micron coatings, as the plasma coating tends toprovide a smoother surface.

VII.A.2.a. Still another embodiment is a method of applying a coating ofa lubricity and/or hydrophobic layer on an elastomeric stopper. Thestopper can be used, for example, to close the vessel previouslydescribed. The method includes several parts. A stopper is placed in asubstantially evacuated chamber. A reaction mixture is providedcomprising plasma forming gas, i.e. an organosilicon compound gas,optionally an oxidizing gas, and optionally a hydrocarbon gas. Plasma isformed in the reaction mixture. The stopper is contacted with thereaction mixture, depositing the coating of a lubricity and/orhydrophobic layer on at least a portion of the stopper.

VII.A.2.a. In practicing this method, to obtain higher values of y and zas defined in the Definition Section, it is contemplated that thereaction mixture can comprise a hydrocarbon gas, as further describedabove and below. Optionally, the reaction mixture can contain oxygen, iflower values of y and z or higher values of x are contemplated. Or,particularly to reduce oxidation and increase the values of y and z, thereaction mixture can be essentially free of an oxidizing gas.

VII.A.2.a. In practicing this method to coat certain embodiments of thestopper such as the stopper 282, it is contemplated to be unnecessary toproject the reaction mixture into the concavities of the stopper. Forexample, the wall-contacting and interior facing surfaces 276 and 272 ofthe stopper 282 are essentially convex, and thus readily treated by abatch process in which a multiplicity of stoppers such as 282 can belocated and treated in a single substantially evacuated reactionchamber. It is further contemplated that in some embodiments thecoatings 286 and 288 do not need to present as formidable a barrier tooxygen or water as the barrier layer on the interior surface 280 of thevessel 268, as the material of the stopper 282 can serve this functionto a large degree.

VII.A.2.a. Many variations of the stopper and the stopper coatingprocess are contemplated. The stopper 282 can be contacted with theplasma. Or, the plasma can be formed upstream of the stopper 282,producing plasma product, and the plasma product can be contacted withthe stopper 282. The plasma can be formed by exciting the reactionmixture with electromagnetic energy and/or microwave energy.

VII.A.2.a. Variations of the reaction mixture are contemplated. Theplasma forming gas can include an inert gas. The inert gas can be, forexample, argon or helium, or other gases described in this disclosure.The organosilicon compound gas can be, or include, HMDSO, OMCTS, any ofthe other organosilicon compounds mentioned in this disclosure, or acombination of two or more of these. The oxidizing gas can be oxygen orthe other gases mentioned in this disclosure, or a combination of two ormore of these. The hydrocarbon gas can be, for example, methane,methanol, ethane, ethylene, ethanol, propane, propylene, propanol,acetylene, or a combination of two or more of these.

VII.A.2.b. Applying by PECVD a Coating of Group III or IV Element andCarbon on a Stopper

VII.A.2.b. Another embodiment is a method of applying a coating of acomposition including carbon and one or more elements of Groups III orIV on an elastomeric stopper. To carry out the method, a stopper islocated in a deposition chamber.

VII.A.2.b. A reaction mixture is provided in the deposition chamber,including a plasma forming gas with a gaseous source of a Group IIIelement, a Group IV element, or a combination of two or more of these.The reaction mixture optionally contains an oxidizing gas and optionallycontains a gaseous compound having one or more C—H bonds. Plasma isformed in the reaction mixture, and the stopper is contacted with thereaction mixture. A coating of a Group III element or compound, a GroupIV element or compound, or a combination of two or more of these isdeposited on at least a portion of the stopper.

VII.A.3. Stoppered Plastic Vessel Having Barrier Layer Effective toProvide 95% Vacuum Retention for 24 Months

VII.A.3. Another embodiment is a vessel including a barrier layer and aclosure. The vessel is generally tubular and made of thermoplasticmaterial. The vessel has a mouth and a lumen bounded at least in part bya wall. The wall has an inner surface interfacing with the lumen. An atleast essentially continuous barrier layer is applied on the innersurface of the wall. The barrier layer is effective to provide asubstantial shelf life. A closure is provided covering the mouth of thevessel and isolating the lumen of the vessel from ambient air.

VII.A.3. Referring to FIGS. 23-25, a vessel 268 such as an evacuatedblood collection tube or other vessel is shown.

VII.A.3. The vessel is, in this embodiment, a generally tubular vesselhaving an at least essentially continuous barrier layer and a closure.The vessel is made of thermoplastic material having a mouth and a lumenbounded at least in part by a wall having an inner surface interfacingwith the lumen. The barrier layer is deposited on the inner surface ofthe wall, and is effective to maintain at least 95%, or at least 90%, ofthe initial vacuum level of the vessel for a shelf life of at least 24months, optionally at least 30 months, optionally at least 36 months.The closure covers the mouth of the vessel and isolates the lumen of thevessel from ambient air.

VII.A.3. The closure, for example the closure 270 illustrated in theFigures or another type of closure, is provided to maintain a partialvacuum and/or to contain a sample and limit or prevent its exposure tooxygen or contaminants. FIGS. 23-25 are based on figures found in U.S.Pat. No. 6,602,206, but the present discovery is not limited to that orany other particular type of closure.

VII.A.3. The closure 270 comprises a interior-facing surface 272 exposedto the lumen 274 of the vessel 268 and a wall-contacting surface 276that is in contact with the inner surface 278 of the vessel wall 280. Inthe illustrated embodiment the closure 270 is an assembly of a stopper282 and a shield 284.

VII.A.3. In the illustrated embodiment, the stopper 282 defines thewall-contacting surface 276 and the inner surface 278, while the shieldis largely or entirely outside the stoppered vessel 268, retains andprovides a grip for the stopper 282, and shields a person removing theclosure 270 from being exposed to any contents expelled from the vessel268, such as due to a pressure difference inside and outside of thevessel 268 when the vessel 268 is opened and air rushes in or out toequalize the pressure difference.

VII.A.3. It is further contemplated that the coatings on the vessel wall280 and the wall contacting surface 276 of the stopper can becoordinated. The stopper can be coated with a lubricity silicone layer,and the vessel wall 280, made for example of PET or glass, can be coatedwith a harder SiO_(x) layer, or with an underlying SiO.sub.x layer and alubricity overcoat.

VII.B. Syringes

VII.B. The foregoing description has largely addressed applying abarrier layer to a tube with one permanently closed end, such as a bloodcollection tube or, more generally, a specimen receiving tube 80. Theapparatus is not limited to such a device.

VII.B. Another example of a suitable vessel, shown in FIGS. 20-22, is asyringe barrel 250 for a medical syringe 252. Such syringes 252 aresometimes supplied prefilled with saline solution, a pharmaceuticalpreparation, or the like for use in medical techniques. Pre-filledsyringes 252 are also contemplated to benefit from an SiO_(x) barrier orother type of coating on the interior surface 254 to keep the contentsof the prefilled syringe 252 out of contact with the plastic of thesyringe, for example of the syringe barrel 250 during storage. Thebarrier or other type of coating can be used to avoid leachingcomponents of the plastic into the contents of the barrel through theinterior surface 254.

VII.B. A syringe barrel 250 as molded commonly can be open at both theback end 256, to receive a plunger 258, and at the front end 260, toreceive a hypodermic needle, a nozzle, or tubing for dispensing thecontents of the syringe 252 or for receiving material into the syringe252. But the front end 260 can optionally be capped and the plunger 258optionally can be fitted in place before the prefilled syringe 252 isused, closing the barrel 250 at both ends. A cap 262 can be installedeither for the purpose of processing the syringe barrel 250 or assembledsyringe, or to remain in place during storage of the prefilled syringe252, up to the time the cap 262 is removed and (optionally) a hypodermicneedle or other delivery conduit is fitted on the front end 260 toprepare the syringe 252 for use.

VII.B.1. Assemblies

VII.B.1. FIG. 42 also shows an alternative syringe barrel constructionusable, for example, with the embodiments of FIGS. 21, 26, 28, 30, and34 and adapted for use with the vessel holder 450 of that Figure.

VII.B.1. FIG. 50 is an exploded view and FIG. 51 is an assembled view ofa syringe. The syringe barrel can be processed with the vessel treatmentand inspection apparatus of FIGS. 1-22, 26-28, 33-35, 37-39, 44, and53-54.

VII.B.1. The installation of a cap 262 makes the barrel 250 a closed-endvessel that can be provided with an SiO_(x) barrier or other type ofcoating on its interior surface 254 in the previously illustratedapparatus, optionally also providing a coating on the interior 264 ofthe cap and bridging the interface between the cap interior 264 and thebarrel front end 260. Suitable apparatus adapted for this use is shown,for example, in FIG. 21, which is analogous to FIG. 2 except for thesubstitution of the capped syringe barrel 250 for the vessel 80 of FIG.2. VII.B.

VII.B.1 FIG. 52 is a view similar to FIG. 42, but showing a syringebarrel being treated that has no flange or finger stops 440. The syringebarrel is usable with the vessel treatment and inspection apparatus ofFIGS. 1-19, 27, 33, 35, 44-51, and 53-54.

VII.B.1.a. Syringe Having Barrel Coated with Lubricity Layer Depositedfrom an Organosilicon Precursor

VII.B.1.a. Still another embodiment is a vessel having a lubricitylayer, characterized as defined in the Definition Section, of the typemade by the following process.

VII.B.1.a. A precursor is provided as defined above.

VII.B.1.a. The precursor is applied to a substrate under conditionseffective to form a coating. The coating is polymerized or crosslinked,or both, to form a lubricated surface having a lower plunger slidingforce or breakout force than the untreated substrate.

VII.B.1.a. Respecting any of the Embodiments VII and sub-parts,optionally the applying step is carried out by vaporizing the precursorand providing it in the vicinity of the substrate.

VII.B.1.a. Respecting any of the Embodiments VII.A.1.a.i, optionally aplasma, optionally a non-hollow-cathode plasma, is formed in thevicinity of the substrate. Optionally, the precursor is provided in thesubstantial absence of oxygen. Optionally, the precursor is provided inthe substantial absence of a carrier gas. Optionally, the precursor isprovided in the substantial absence of nitrogen. Optionally, theprecursor is provided at less than 1 Torr absolute pressure. Optionally,the precursor is provided to the vicinity of a plasma emission.Optionally, the precursor its reaction product is applied to thesubstrate at a thickness of 1 to 5000 nm thick, or 10 to 1000 nm thick,or 10-200 nm thick, or 20 to 100 nm thick. Optionally, the substratecomprises glass. Optionally, the substrate comprises a polymer,optionally a polycarbonate polymer, optionally an olefin polymer,optionally a cyclic olefin copolymer, optionally a polypropylenepolymer, optionally a polyester polymer, optionally a polyethyleneterephthalate polymer.

VII.B.1.a. Optionally, the plasma is generated by energizing the gaseousreactant containing the precursor with electrodes powered, for example,at a RF frequency as defined above, for example a frequency of from 10kHz to less than 300 MHz, optionally from 1 to 50 MHz, even optionallyfrom 10 to 15 MHz, optionally a frequency of 13.56 MHz.

VII.B.1.a. Optionally, the plasma is generated by energizing the gaseousreactant containing the precursor with electrodes supplied with anelectric power of from 0.1 to 25 W, optionally from 1 to 22 W,optionally from 3 to 17 W, even optionally from 5 to 14 W, optionallyfrom 7 to 11 W, optionally 8 W. The ratio of the electrode power to theplasma volume can be less than 10 W/ml, optionally is from 5 W/ml to 0.1W/ml, optionally is from 4 W/ml to 0.1 W/ml, optionally from 2 W/ml to0.2 W/ml. These power levels are suitable for applying lubricity layersto syringes and sample tubes and vessels of similar geometry having avoid volume of 1 to 3 mL in which PECVD plasma is generated. It iscontemplated that for larger or smaller objects the power applied shouldbe increased or reduced accordingly to scale the process to the size ofthe substrate.

VII.B.1.a. Another embodiment is a lubricity layer, characterized asdefined in the Definition Section, on the inner wall of a syringebarrel. The coating is produced from a PECVD process using the followingmaterials and conditions. A cyclic precursor is optionally employed,selected from a monocyclic siloxane, a polycyclic siloxane, or acombination of two or more of these, as defined elsewhere in thisspecification for lubricity layers. One example of a suitable cyclicprecursor comprises octamethylcyclotetrasiloxane (OMCTS), optionallymixed with other precursor materials in any proportion. Optionally, thecyclic precursor consists essentially of octamethylcyclotetrasiloxane(OMCTS), meaning that other precursors can be present in amounts whichdo not change the basic and novel properties of the resulting lubricitylayer, i.e. its reduction of the plunger sliding force or breakout forceof the coated surface.

VII.B.1.a. At least essentially no oxygen. as defined in the DefinitionSection is added to the process.

VII.B.1.a. A sufficient plasma generation power input, for example anypower level successfully used in one or more working examples of thisspecification or described in the specification, is provided to inducecoating formation.

VII.B.1.a. The materials and conditions employed are effective to reducethe syringe plunger sliding force or breakout force moving through thesyringe barrel at least 25 percent, alternatively at least 45 percent,alternatively at least 60 percent, alternatively greater than 60percent, relative to an uncoated syringe barrel. Ranges of plungersliding force or breakout force reduction of from 20 to 95 percent,alternatively from 30 to 80 percent, alternatively from 40 to 75percent, alternatively from 60 to 70 percent, are contemplated.

VII.B.1.a. Another embodiment is a vessel having a hydrophobic layer,characterized as defined in the Definition Section, on the inside wall.The coating is made as explained for the lubricant coating of similarcomposition, but under conditions effective to form a hydrophobicsurface having a higher contact angle than the untreated substrate.

VII.B.1.a. Respecting any of the Embodiments VII.A.1.a.ii, optionallythe substrate comprises glass or a polymer. The glass optionally isborosilicate glass. The polymer is optionally a polycarbonate polymer,optionally an olefin polymer, optionally a cyclic olefin copolymer,optionally a polypropylene polymer, optionally a polyester polymer,optionally a polyethylene terephthalate polymer.

VII.B.1.a. Another embodiment is a syringe including a plunger, asyringe barrel, and a lubricity layer, characterized as defined in theDefinition Section. The syringe barrel includes an interior surfacereceiving the plunger for sliding. The lubricity layer is disposed onthe interior surface of the syringe barrel. The lubricity layer is lessthan 1000 nm thick and effective to reduce the breakout force or theplunger sliding force necessary to move the plunger within the barrel.Reducing the plunger sliding force is alternatively expressed asreducing the coefficient of sliding friction of the plunger within thebarrel or reducing the plunger force; these terms are regarded as havingthe same meaning in this specification.

VII.B.1.a. The syringe 544 of FIGS. 50-51 comprises a plunger 546 and asyringe barrel 548. The syringe barrel 548 has an interior surface 552receiving the plunger for sliding 546. The interior surface 552 of thesyringe barrel 548 further comprises a lubricity layer 554,characterized as defined in the Definition Section. The lubricity layeris less than 1000 nm thick, optionally less than 500 nm thick,optionally less than 200 nm thick, optionally less than 100 nm thick,optionally less than 50 nm thick, and is effective to reduce thebreakout force necessary to overcome adhesion of the plunger afterstorage or the plunger sliding force necessary to move the plungerwithin the barrel after it has broken away. The lubricity layer ischaracterized by having a plunger sliding force or breakout force lowerthan that of the uncoated surface.

VII.B.1.a. Any of the above precursors of any type can be used alone orin combinations of two or more of them to provide a lubricity layer.

VII.B.1.a. In addition to utilizing vacuum processes, low temperatureatmospheric (non-vacuum) plasma processes can also be utilized to inducemolecular ionization and deposition through precursor monomer vapordelivery optionally in a non-oxidizing atmosphere such as helium orargon. Separately, thermal CVD can be considered via flash thermolysisdeposition.

VII.B.1.a. The approaches above are similar to vacuum PECVD in that thesurface coating and crosslinking mechanisms can occur simultaneously.

VII.B.1.a. Yet another expedient contemplated for any coating orcoatings described here is a coating that is not uniformly applied overthe entire interior 88 of a vessel. For example, a different oradditional coating can be applied selectively to the cylindrical portionof the vessel interior, compared to the hemispherical portion of thevessel interior at its closed end 84, or vice versa. This expedient isparticularly contemplated for a syringe barrel or a sample collectiontube as described below, in which a lubricity layer might be provided onpart or all of the cylindrical portion of the barrel, where the plungeror piston or closure slides, and not elsewhere.

VII.B.1.a. Optionally, the precursor can be provided in the presence,substantial absence, or absence of oxygen, in the presence, substantialabsence, or absence of nitrogen, or in the presence, substantialabsence, or absence of a carrier gas. In one contemplated embodiment,the precursor alone is delivered to the substrate and subjected to PECVDto apply and cure the coating.

VII.B.1.a. Optionally, the precursor can be provided at less than 1 Torrabsolute pressure.

VII.B.1.a. Optionally, the precursor can be provided to the vicinity ofa plasma emission.

VII.B.1.a. Optionally, the precursor its reaction product can be appliedto the substrate at a thickness of 1 to 5000 nm, or 10 to 1000 nm., or10-200 nm, or 20 to 100 nm.

VII.B.1.a. In any of the above embodiments, the substrate can compriseglass, or a polymer, for example one or more of a polycarbonate polymer,an olefin polymer (for example a cyclic olefin copolymer or apolypropylene polymer), or a polyester polymer (for example, apolyethylene terephthalate polymer).

VII.B.1.a. In any of the above embodiments, the plasma is generated byenergizing the gaseous reactant containing the precursor with electrodespowered at a RF frequency as defined in this description.

VII.B.1.a. In any of the above embodiments, the plasma is generated byenergizing the gaseous reactant containing the precursor with electrodessupplied with sufficient electric power to generate a lubricity layer.Optionally, the plasma is generated by energizing the gaseous reactantcontaining the precursor with electrodes supplied with an electric powerof from 0.1 to 25 W, optionally from 1 to 22 W, optionally from 3 to 17W, even optionally from 5 to 14 W, optionally from 7 to 11 W, optionally8 W. The ratio of the electrode power to the plasma volume can be lessthan 10 W/ml, optionally is from 5 W/ml to 0.1 W/ml, optionally is from4 W/ml to 0.1 W/ml, optionally from 2 W/ml to 0.2 W/ml. These powerlevels are suitable for applying lubricity layers to syringes and sampletubes and vessels of similar geometry having a void volume of 1 to 3 mLin which PECVD plasma is generated. It is contemplated that for largeror smaller objects the power applied should be increased or reducedaccordingly to scale the process to the size of the substrate.

VII.B.1.a. The coating can be cured, as by polymerizing or crosslinkingthe coating, or both, to form a lubricated surface having a lowerplunger sliding force or breakout force than the untreated substrate.Curing can occur during the application process such as PECVD, or can becarried out or at least completed by separate processing.

VII.B.1.a. Although plasma deposition has been used herein todemonstrate the coating characteristics, alternate deposition methodscan be used as long as the chemical composition of the starting materialis preserved as much as possible while still depositing a solid filmthat is adhered to the base substrate.

VII.B.1.a. For example, the coating material can be applied onto thesyringe barrel (from the liquid state) by spraying the coating ordipping the substrate into the coating, where the coating is either theneat precursor a solvent-diluted precursor (allowing the mechanicaldeposition of a thinner coating). The coating optionally can becrosslinked using thermal energy, UV energy, electron beam energy,plasma energy, or any combination of these.

VII.B.1.a. Application of a silicone precursor as described above onto asurface followed by a separate curing step is also contemplated. Theconditions of application and curing can be analogous to those used forthe atmospheric plasma curing of pre-coated polyfluoroalkyl ethers, aprocess practiced under the trademark TriboGlide®. More details of thisprocess can be found at http://www.triboglide.com/process.htm.

VII.B.1.a. In such a process, the area of the part to be coated canoptionally be pre-treated with an atmospheric plasma. This pretreatmentcleans and activates the surface so that it is receptive to thelubricant that is sprayed in the next step.

VII.B.1.a. The lubrication fluid, in this case one of the aboveprecursors or a polymerized precursor, is then sprayed on to the surfaceto be treated. For example, IVEK precision dispensing technology can beused to accurately atomize the fluid and create a uniform coating.

VII.B.1.a. The coating is then bonded or crosslinked to the part, againusing an atmospheric plasma field. This both immobilizes the coating andimproves the lubricant's performance.

VII.B.1.a. Optionally, the atmospheric plasma can be generated fromambient air in the vessel, in which case no gas feed and no vacuumdrawing equipment is needed. Optionally, however, the vessel is at leastsubstantially closed while plasma is generated, to minimize the powerrequirement and prevent contact of the plasma with surfaces or materialsoutside the vessel.

VII.B.1.a.i. Lubricity Layer: SiO_(x) Barrier, Lubricity Layer, SurfaceTreatment

Surface Treatment

VII.B.1.a.i. Another embodiment is a syringe comprising a barreldefining a lumen and having an interior surface slidably receiving aplunger, i.e. receiving a plunger for sliding contact to the interiorsurface.

VII.B.1.a.i. The syringe barrel is made of thermoplastic base material.

VII.B.1.a.i. Optionally, the interior surface of the barrel is coatedwith an SiO_(x) barrier layer as described elsewhere in thisspecification.

VII.B.1.a.i. A lubricity layer is applied to the barrel interiorsurface, the plunger, or both, or to the previously applied SiO_(x)barrier layer. The lubricity layer can be provided, applied, and curedas set out in embodiment VII.B.1.a or elsewhere in this specification.

VII.B.1.a.i. For example, the lubricity layer can be applied, in anyembodiment, by PECVD. The lubricity layer is deposited from anorganosilicon precursor, and is less than 1000 nm thick.

VII.B.1.a.i. A surface treatment is carried out on the lubricity layerin an amount effective to reduce the leaching or extractables of thelubricity layer, the thermoplastic base material, or both. The treatedsurface can thus act as a solute retainer. This surface treatment canresult in a skin coating, e.g. a skin coating which is at least 1 nmthick and less than 100 nm thick, or less than 50 nm thick, or less than40 nm thick, or less than 30 nm thick, or less than 20 nm thick, or lessthan 10 nm thick, or less than 5 nm thick, or less than 3 nm thick, orless than 2 nm thick, or less than 1 nm thick, or less than 0.5 nmthick.

VII.B.1.a.i. As used herein, “leaching” refers to material transferredout of a substrate, such as a vessel wall, into the contents of avessel, for example a syringe. Commonly, leachables are measured bystoring the vessel filled with intended contents, then analyzing thecontents to determine what material leached from the vessel wall intothe intended contents. “Extraction” refers to material removed from asubstrate by introducing a solvent or dispersion medium other than theintended contents of the vessel, to determine what material can beremoved from the substrate into the extraction medium under theconditions of the test.

VII.B.1.a.i. The surface treatment resulting in a solute retaineroptionally can be a SiO_(x) layer as previously defined in thisspecification or a hydrophobic layer, characterized as defined in theDefinition Section. In one embodiment, the surface treatment can beapplied by PECVD deposit of SiO_(x) or a hydrophobic layer. Optionally,the surface treatment can be applied using higher power or strongeroxidation conditions than used for creating the lubricity layer, orboth, thus providing a harder, thinner, continuous solute retainer 539.Surface treatment can be less than 100 nm deep, optionally less than 50nm deep, optionally less than 40 nm deep, optionally less than 30 nmdeep, optionally less than 20 nm deep, optionally less than 10 nm deep,optionally less than 5 nm deep, optionally less than 3 nm deep,optionally less than 1 nm deep, optionally less than 0.5 nm deep,optionally between 0.1 and 50 nm deep in the lubricity layer.

VII.B.1.a.i. The solute retainer is contemplated to provide low soluteleaching performance to the underlying lubricity and other layers,including the substrate, as required. This retainer would only need tobe a solute retainer to large solute molecules and oligomers (forexample siloxane monomers such as HMDSO, OMCTS, their fragments andmobile oligomers derived from lubricants, for example a “leachablesretainer”) and not a gas (O₂/N₂/CO₂/water vapor) barrier layer. A soluteretainer can, however, also be a gas barrier (e.g. the SiO_(x) coatingaccording to present invention. One can create a good leachable retainerwithout gas barrier performance, either by vacuum or atmospheric-basedPECVD processes. It is desirable that the “leachables barrier” will besufficiently thin that, upon syringe plunger movement, the plunger willreadily penetrate the “solute retainer” exposing the sliding plungernipple to the lubricity layer immediately below to form a lubricatedsurface having a lower plunger sliding force or breakout force than theuntreated substrate.

VII.B.1.a.i. In another embodiment, the surface treatment can beperformed by oxidizing the surface of a previously applied lubricitylayer, as by exposing the surface to oxygen in a plasma environment. Theplasma environment described in this specification for forming SiO_(x)coatings can be used. Or, atmospheric plasma conditions can be employedin an oxygen-rich environment.

VII.B.1.a.i. The lubricity layer and solute retainer, however formed,optionally can be cured at the same time. In another embodiment, thelubricity layer can be at least partially cured, optionally fully cured,after which the surface treatment can be provided, applied, and thesolute retainer can be cured.

VII.B.1.a.i. The lubricity layer and solute retainer are composed, andpresent in relative amounts, effective to provide a breakout force,plunger sliding force, or both that is less than the corresponding forcerequired in the absence of the lubricity layer and surface treatment. Inother words, the thickness and composition of the solute retainer aresuch as to reduce the leaching of material from the lubricity layer intothe contents of the syringe, while allowing the underlying lubricitylayer to lubricate the plunger. It is contemplated that the soluteretainer will break away easily and be thin enough that the lubricitylayer will still function to lubricate the plunger when it is moved.

VII.B.1.a.i. In one contemplated embodiment, the lubricity and surfacetreatments can be applied on the barrel interior surface. In anothercontemplated embodiment, the lubricity and surface treatments can beapplied on the plunger. In still another contemplated embodiment, thelubricity and surface treatments can be applied both on the barrelinterior surface and on the plunger. In any of these embodiments, theoptional SiO_(x) barrier layer on the interior of the syringe barrel caneither be present or absent.

VII.B.1.a.i. One embodiment contemplated is a plural-layer, e.g. a3-layer, configuration applied to the inside surface of a syringebarrel. Layer 1 can be an SiO_(x) gas barrier made by PECVD of HMDSO,OMCTS, or both, in an oxidizing atmosphere. Such an atmosphere can beprovided, for example, by feeding HMDSO and oxygen gas to a PECVDcoating apparatus as described in this specification. Layer 2 can be alubricity layer using OMCTS applied in a non-oxidizing atmosphere. Sucha non-oxidizing atmosphere can be provided, for example, by feedingOMCTS to a PECVD coating apparatus as described in this specification,optionally in the substantial or complete absence of oxygen. Asubsequent solute retainer can be formed by a treatment forming a thinskin layer of SiO_(x) or a hydrophobic layer as a solute retainer usinghigher power and oxygen using OMCTS and/or HMDSO.

VII.B.1.a.i. Certain of these plural-layer coatings are contemplated tohave one or more of the following optional advantages, at least to somedegree. They can address the reported difficulty of handling silicone,since the solute retainer can confine the interior silicone and preventit from migrating into the contents of the syringe or elsewhere,resulting in fewer silicone particles in the deliverable contents of thesyringe and less opportunity for interaction between the lubricity layerand the contents of the syringe. They can also address the issue ofmigration of the lubricity layer away from the point of lubrication,improving the lubricity of the interface between the syringe barrel andthe plunger. For example, the break-free force can be reduced and thedrag on the moving plunger can be reduced, or optionally both.

VII.B.1.a.i. It is contemplated that when the solute retainer is broken,the solute retainer will continue to adhere to the lubricity layer andthe syringe barrel, which can inhibit any particles from being entrainedin the deliverable contents of the syringe.

VII.B.1.a.i. Certain of these coatings will also provide manufacturingadvantages, particularly if the barrier layer, lubricity layer andsurface treatment are applied in the same apparatus, for example theillustrated PECVD apparatus. Optionally, the SiO_(x) barrier layer,lubricity layer, and surface treatment can all be applied in one PECVDapparatus, thus greatly reducing the amount of handling necessary.

Further advantages can be obtained by forming the barrier layer,lubricity layer, and solute retainer using the same precursors andvarying the process. For example, an SiO_(x) gas barrier layer can beapplied using an OMCTS precursor under high power/high O₂ conditions,followed by applying a lubricity layer applied using an OMCTS precursorunder low power and/or in the substantial or complete absence of oxygen,finishing with a surface treatment using an OMCTS precursor underintermediate power and oxygen.

VII.B.1.b Syringe Having Barrel with SiO_(x) Coated Interior and BarrierCoated Exterior

VII.B.1.b. Still another embodiment, illustrated in FIG. 50, is asyringe 544 including a plunger 546, a barrel 548, and interior andexterior barrier layers 554 and 602. The barrel 548 can be made ofthermoplastic base material defining a lumen 604. The barrel 548 canhave an interior surface 552 receiving the plunger for sliding 546 andan exterior surface 606. A barrier layer 554 of SiO_(x), in which x isfrom about 1.5 to about 2.9, can be provided on the interior surface 552of the barrel 548. A barrier layer 602 of a resin can be provided on theexterior surface 606 of the barrel 548.

VII.B.1.b. In any embodiment, the thermoplastic base material optionallycan include a polyolefin, for example polypropylene or a cyclic olefincopolymer (for example the material sold under the trademark TOPAS®), apolyester, for example polyethylene terephthalate, a polycarbonate, forexample a bisphenol A polycarbonate thermoplastic, or other materials.Composite syringe barrels are contemplated having any one of thesematerials as an outer layer and the same or a different one of thesematerials as an inner layer. Any of the material combinations of thecomposite syringe barrels or sample tubes described elsewhere in thisspecification can also be used.

VII.B.1.b. In any embodiment, the resin optionally can includepolyvinylidene chloride in homopolymer or copolymer form. For example,the PVdC homopolymers (trivial name: Saran) or copolymers described inU.S. Pat. No. 6,165,566, incorporated here by reference, can beemployed. The resin optionally can be applied onto the exterior surfaceof the barrel in the form of a latex or other dispersion.

VII.B.1.b. In any embodiment, the syringe barrel 548 optionally caninclude a lubricity layer disposed between the plunger and the barrierlayer of SiO_(x). Suitable lubricity layers are described elsewhere inthis specification.

VII.B.1.b. In any embodiment, the lubricity layer optionally can beapplied by PECVD and optionally can include material characterized asdefined in the Definition Section.

VII.B.1.b. In any embodiment, the syringe barrel 548 optionally caninclude a surface treatment covering the lubricity layer in an amounteffective to reduce the leaching of the lubricity layer, constituents ofthe thermoplastic base material, or both into the lumen 604.

VII.B.1.c Method of Making Syringe Having Barrel with SiO_(x) CoatedInterior and Barrier Coated Exterior

VII.B.1.c. Even another embodiment is a method of making a syringe asdescribed in any of the embodiments of part VII.B.1.b, including aplunger, a barrel, and interior and exterior barrier layers. A barrel isprovided having an interior surface for receiving the plunger forsliding and an exterior surface. A barrier layer of SiO_(x) is providedon the interior surface of the barrel by PECVD. A barrier layer of aresin is provided on the exterior surface of the barrel. The plunger andbarrel are assembled to provide a syringe.

VII.B.1.c. For effective coating (uniform wetting) of the plasticarticle with the aqueous latex, it is contemplated to be useful to matchthe surface tension of the latex to the plastic substrate. This can beaccomplished by several approaches, independently or combined, forexample, reducing the surface tension of the latex (with surfactants orsolvents), and/or corona pretreatment of the plastic article, and/orchemical priming of the plastic article.

VII.B.1.c. The resin optionally can be applied via dip coating of thelatex onto the exterior surface of the barrel, spray coating of thelatex onto the exterior surface of the barrel, or both, providingplastic-based articles offering improved gas and vapor barrierperformance. Polyvinylidene chloride plastic laminate articles can bemade that provide significantly improved gas barrier performance versusthe non-laminated plastic article.

VII.B.1.c. In any embodiment, the resin optionally can be heat cured.The resin optionally can be cured by removing water. Water can beremoved by heat curing the resin, exposing the resin to a partial vacuumor low-humidity environment, catalytically curing the resin, or otherexpedients.

VII.B.1.c. An effective thermal cure schedule is contemplated to providefinal drying to permit PVdC crystallization, offering barrierperformance. Primary curing can be carried out at an elevatedtemperature, for example between 180-310.degree. F. (82-154.degree. C.),of course depending on the heat tolerance of the thermoplastic basematerial. Barrier performance after the primary cure optionally can beabout 85% of the ultimate barrier performance achieved after a finalcure.

VII.B.1.c. A final cure can be carried out at temperatures ranging fromambient temperature, such as about 65-75.degree. F. (18-24.degree. C.)for a long time (such as 2 weeks) to an elevated temperature, such as122.degree. F. (50.degree. C.), for a short time, such as four hours.

VII.B.1.c. The PVdC-plastic laminate articles, in addition to superiorbarrier performance, are optionally contemplated to provide one or moredesirable properties such as colorless transparency, good gloss,abrasion resistance, printability, and mechanical strain resistance.

VII.B.2. Plungers

VII.B.2.a. With Barrier Coated Piston Front Face

VII.B.2.a. Another embodiment is a plunger for a syringe, including apiston and a push rod. The piston has a front face, a generallycylindrical side face, and a back portion, the side face beingconfigured to movably seat within a syringe barrel. The front face has abarrier layer. The push rod engages the back portion and is configuredfor advancing the piston in a syringe barrel.

VII.B.2.b. With Lubricity Layer Interfacing with Side Face

VII.B.2.b. Yet another embodiment is a plunger for a syringe, includinga piston, a lubricity layer, and a push rod. The piston has a frontface, a generally cylindrical side face, and a back portion. The sideface is configured to movably seat within a syringe barrel. Thelubricity layer interfaces with the side face. The push rod engages theback portion of the piston and is configured for advancing the piston ina syringe barrel.

VII.B.3. Two Piece Syringe and Luer Fitting

VII.B.3. Another embodiment is a syringe including a plunger, a syringebarrel, and a Luer fitting. The syringe includes a barrel having aninterior surface receiving the plunger for sliding. The Luer fittingincludes a Luer taper having an internal passage defined by an internalsurface. The Luer fitting is formed as a separate piece from the syringebarrel and joined to the syringe barrel by a coupling. The internalpassage of the Luer taper has a barrier layer of SiO_(x).

VII.B.3. Referring to FIGS. 50-51, the syringe 544 optionally caninclude a Luer fitting 556 comprising a Luer taper 558 to receive acannula mounted on a complementary Luer taper (not shown, conventional).The Luer taper 558 has an internal passage 560 defined by an internalsurface 562. The Luer fitting 556 optionally is formed as a separatepiece from the syringe barrel 548 and joined to the syringe barrel 548by a coupling 564. As illustrated in FIGS. 50 and 51, the coupling 564in this instance has a male part 566 and a female part 568 that snaptogether to secure the Luer fitting in at least substantially leak prooffashion to the barrel 548. The internal surface 562 of the Luer tapercan include a barrier layer 570 of SiO_(x). The barrier layer can beless than 100 nm thick and effective to reduce the ingress of oxygeninto the internal passage of the Luer fitting. The barrier layer can beapplied before the Luer fitting is joined to the syringe barrel. Thesyringe of FIGS. 50-51 also has an optional locking collar 572 that isinternally threaded so to lock the complementary Luer taper of a cannulain place on the taper 558.

VII.B.4. Lubricant Compositions—Lubricity layer Deposited from anOrganosilicon Precursor Made by In Situ Polymerizing OrganosiliconPrecursor VII.B.4.a. Product by Process and Lubricity

VII.B.4.a. Still another embodiment is a lubricity layer. This coatingcan be of the type made by the following process.

VII.B.4.a. Any of the precursors mentioned elsewhere in thisspecification can be used, alone or in combination. The precursor isapplied to a substrate under conditions effective to form a coating. Thecoating is polymerized or crosslinked, or both, to form a lubricatedsurface having a lower plunger sliding force or breakout force than theuntreated substrate.

VII.B.4.a. Another embodiment is a method of applying a lubricity layer.An organosilicon precursor is applied to a substrate under conditionseffective to form a coating. The coating is polymerized or crosslinked,or both, to form a lubricated surface having a lower plunger slidingforce or breakout force than the untreated substrate.

VII.B.4.b. Product by Process and Analytical Properties

VII.B.4.b. Even another aspect of the invention is a lubricity layerdeposited by PECVD from a feed gas comprising an organometallicprecursor, optionally an organosilicon precursor, optionally a linearsiloxane, a linear silazane, a monocyclic siloxane, a monocyclicsilazane, a polycyclic siloxane, a polycyclic silazane, or anycombination of two or more of these. The coating has a density between1.25 and 1.65 g/cm³ optionally between 1.35 and 1.55 g/cm³, optionallybetween 1.4 and 1.5 g/cm³, optionally between 1.44 and 1.48 g/cm³ asdetermined by X-ray reflectivity (XRR).

VII.B.4.b. Still another aspect of the invention is a lubricity layerdeposited by PECVD from a feed gas comprising an organometallicprecursor, optionally an organosilicon precursor, optionally a linearsiloxane, a linear silazane, a monocyclic siloxane, a monocyclicsilazane, a polycyclic siloxane, a polycyclic silazane, or anycombination of two or more of these. The coating has as an outgascomponent one or more oligomers containing repeating -(Me)₂SiO—moieties, as determined by gas chromatography/mass spectrometry.Optionally, the coating meets the limitations of any of embodimentsVII.B.4.a or VII.B.4.b.A.585h. Optionally, the coating outgas componentas determined by gas chromatography/mass spectrometry is substantiallyfree of trimethylsilanol.

VII.B.4.b. Optionally, the coating outgas component can be at least 10ng/test of oligomers containing repeating -(Me)₂SiO— moieties, asdetermined by gas chromatography/mass spectrometry using the followingtest conditions:

-   -   GC Column 30 m×0.25 mm DB-5MS (J&W Scientific), 0.25 μm film        thickness    -   Flow rate: 1.0 ml/min, constant flow mode    -   Detector: Mass Selective Detector (MSD)    -   Injection mode: Split injection (10:1 split ratio)    -   Outgassing Conditions: 1½″ (37 mm) Chamber, purge for three hour        at 85° C., Flow 60 ml/mn    -   Oven temperature 40° C. (5 min) to 300° C. at 10° C./min.; hold        for 5 min at 300° C.

VII.B.4.b. Optionally, the outgas component can include at least 20ng/test of oligomers containing repeating -(Me)₂SiO— moieties.

VII.B.4.b. Optionally, the feed gas comprises a monocyclic siloxane, amonocyclic silazane, a polycyclic siloxane, a polycyclic silazane, orany combination of two or more of these, for example a monocyclicsiloxane, a monocyclic silazane, or any combination of two or more ofthese, for example octamethylcyclotetrasiloxane.

VII.B.4.b. The lubricity layer of any embodiment can have a thicknessmeasured by transmission electron microscopy (TEM) between 1 and 500 nm,optionally between 10 and 500 nm, optionally between 20 and 200 nm,optionally between 20 and 100 nm, optionally between 30 and 100 nm.

VII.B.4.b. Another aspect of the invention is a lubricity layerdeposited by PECVD from a feed gas comprising a monocyclic siloxane, amonocyclic silazane, a polycyclic siloxane, a polycyclic silazane, orany combination of two or more of these. The coating has an atomicconcentration of carbon, normalized to 100% of carbon, oxygen, andsilicon, as determined by X-ray photoelectron spectroscopy (XPS),greater than the atomic concentration of carbon in the atomic formulafor the feed gas. Optionally, the coating meets the limitations ofembodiments VII.B.4.a or VII.B.4.b.A.

VII.B.4.b. Optionally, the atomic concentration of carbon increases byfrom 1 to 80 atomic percent (as calculated and based on the XPSconditions in Example 14), alternatively from 10 to 70 atomic percent,alternatively from 20 to 60 atomic percent, alternatively from 30 to 50atomic percent, alternatively from 35 to 45 atomic percent,alternatively from 37 to 41 atomic percent.

VII.B.4.b. An additional aspect of the invention is a lubricity layerdeposited by PECVD from a feed gas comprising a monocyclic siloxane, amonocyclic silazane, a polycyclic siloxane, a polycyclic silazane, orany combination of two or more of these. The coating has an atomicconcentration of silicon, normalized to 100% of carbon, oxygen, andsilicon, as determined by X-ray photoelectron spectroscopy (XPS), lessthan the atomic concentration of silicon in the atomic formula for thefeed gas. Optionally, the coating meets the limitations of embodimentsVII.B.4.a or VII.B.4.b.A.

VII.B.4.b. Optionally, the atomic concentration of silicon decreases byfrom 1 to 80 atomic percent (as calculated and based on the XPSconditions in Example 14), alternatively from 10 to 70 atomic percent,alternatively from 20 to 60 atomic percent, alternatively from 30 to 55atomic percent, alternatively from 40 to 50 atomic percent,alternatively from 42 to 46 atomic percent.

VII.B.4.b. Lubricity layers having combinations of any two or moreproperties recited in Section VII.B.4 are also expressly contemplated.

VII.C. Vessels Generally

VII.C. A coated vessel or container as described herein and/or preparedaccording to a method described herein can be used for reception and/orstorage and/or delivery of a compound or composition. The compound orcomposition can be sensitive, for example air-sensitive,oxygen-sensitive, sensitive to humidity and/or sensitive to mechanicalinfluences. It can be a biologically active compound or composition, forexample a medicament like insulin or a composition comprising insulin.In another aspect, it can be a biological fluid, optionally a bodilyfluid, for example blood or a blood fraction. In certain aspects of thepresent invention, the compound or composition is a product to beadministrated to a subject in need thereof, for example a product to beinjected, like blood (as in transfusion of blood from a donor to arecipient or reintroduction of blood from a patient back to the patient)or insulin.

VII.C. A coated vessel or container as described herein and/or preparedaccording to a method described herein can further be used forprotecting a compound or composition contained in its interior spaceagainst mechanical and/or chemical effects of the surface of theuncoated vessel material. For example, it can be used for preventing orreducing precipitation and/or clotting or platelet activation of thecompound or a component of the composition, for example insulinprecipitation or blood clotting or platelet activation.

VII.C. It can further be used for protecting a compound or compositioncontained in its interior against the environment outside of the vessel,for example by preventing or reducing the entry of one or more compoundsfrom the environment surrounding the vessel into the interior space ofthe vessel. Such environmental compound can be a gas or liquid, forexample an atmospheric gas or liquid containing oxygen, air, and/orwater vapor.

VII.C. A coated vessel as described herein can also be evacuated andstored in an evacuated state. For example, the coating allows bettermaintenance of the vacuum in comparison to a corresponding uncoatedvessel. In one aspect of this embodiment, the coated vessel is a bloodcollection tube. The tube can also contain an agent for preventing bloodclotting or platelet activation, for example EDTA or heparin.

VII.C. Any of the above-described embodiments can be made, for example,by providing as the vessel a length of tubing from about 1 cm to about200 cm, optionally from about 1 cm to about 150 cm, optionally fromabout 1 cm to about 120 cm, optionally from about 1 cm to about 100 cm,optionally from about 1 cm to about 80 cm, optionally from about 1 cm toabout 60 cm, optionally from about 1 cm to about 40 cm, optionally fromabout 1 cm to about 30 cm long, and processing it with a probe electrodeas described below. Particularly for the longer lengths in the aboveranges, it is contemplated that relative motion between the probe andthe vessel can be useful during coating formation. This can be done, forexample, by moving the vessel with respect to the probe or moving theprobe with respect to the vessel.

VII.C. In these embodiments, it is contemplated that the coating can bethinner or less complete than can be preferred for a barrier layer, asthe vessel in some embodiments will not require the high barrierintegrity of an evacuated blood collection tube.

VII.C. As an optional feature of any of the foregoing embodiments thevessel has a central axis.

VII.C. As an optional feature of any of the foregoing embodiments thevessel wall is sufficiently flexible to be flexed at least once at20.degree. C., without breaking the wall, over a range from at leastsubstantially straight to a bending radius at the central axis of notmore than 100 times as great as the outer diameter of the vessel.

VII.C. As an optional feature of any of the foregoing embodiments thebending radius at the central axis is not more than 90 times as greatas, or not more than 80 times as great as, or not more than 70 times asgreat as, or not more than 60 times as great as, or not more than 50times as great as, or not more than 40 times as great as, or not morethan 30 times as great as, or not more than 20 times as great as, or notmore than 10 times as great as, or not more than 9 times as great as, ornot more than 8 times as great as, or not more than 7 times as great as,or not more than 6 times as great as, or not more than 5 times as greatas, or not more than 4 times as great as, or not more than 3 times asgreat as, or not more than 2 times as great as, or not more than, theouter diameter of the vessel.

VII.C. As an optional feature of any of the foregoing embodiments thevessel wall can be a fluid-contacting surface made of flexible material.

VII.C. As an optional feature of any of the foregoing embodiments thevessel lumen can be the fluid flow passage of a pump.

VII.C. As an optional feature of any of the foregoing embodiments thevessel can be a blood bag adapted to maintain blood in good conditionfor medical use.

VII.C., VII.D. As an optional feature of any of the foregoingembodiments the polymeric material can be a silicone elastomer or athermoplastic polyurethane, as two examples, or any material suitablefor contact with blood, or with insulin.

VII.C., VII.D. In an optional embodiment, the vessel has an innerdiameter of at least 2 mm, or at least 4 mm.

VII.C. As an optional feature of any of the foregoing embodiments thevessel is a tube.

VII.C. As an optional feature of any of the foregoing embodiments thelumen has at least two open ends.

VII.C.1. Vessel Containing Viable Blood, Having a Coating Deposited froman Organosilicon Precursor

VII.C.1. Even another embodiment is a blood containing vessel. Severalnon-limiting examples of such a vessel are a blood transfusion bag, ablood sample collection vessel in which a sample has been collected, thetubing of a heart-lung machine, a flexible-walled blood collection bag,or tubing used to collect a patient's blood during surgery andreintroduce the blood into the patient's vasculature. If the vesselincludes a pump for pumping blood, a particularly suitable pump is acentrifugal pump or a peristaltic pump. The vessel has a wall; the wallhas an inner surface defining a lumen. The inner surface of the wall hasan at least partial coating of a hydrophobic layer, characterized asdefined in the Definition Section. The coating can be as thin asmonomolecular thickness or as thick as about 1000 nm. The vesselcontains blood viable for return to the vascular system of a patientdisposed within the lumen in contact with the hydrophobic layer.

VII.C.1. An embodiment is a blood containing vessel including a wall andhaving an inner surface defining a lumen. The inner surface has an atleast partial coating of a hydrophobic layer. The coating can alsocomprise or consist essentially of SiO_(x), where x is as defined inthis specification. The thickness of the coating is within the rangefrom monomolecular thickness to about 1000 nm thick on the innersurface. The vessel contains blood viable for return to the vascularsystem of a patient disposed within the lumen in contact with thehydrophobic layer.

VII.C.2. Coating Deposited from an Organosilicon Precursor ReducesClotting or Platelet Activation of Blood in the Vessel

VII.C.2. Another embodiment is a vessel having a wall. The wall has aninner surface defining a lumen and has an at least partial coating of ahydrophobic layer, where optionally w, x, y, and z are as previouslydefined in the Definition Section. The thickness of the coating is frommonomolecular thickness to about 1000 nm thick on the inner surface. Thecoating is effective to reduce the clotting or platelet activation ofblood exposed to the inner surface, compared to the same type of walluncoated with a hydrophobic layer.

VII.C.2. It is contemplated that the incorporation of a hydrophobiclayer will reduce the adhesion or clot forming tendency of the blood, ascompared to its properties in contact with an unmodified polymeric orSiO_(x) surface. This property is contemplated to reduce or potentiallyeliminate the need for treating the blood with heparin, as by reducingthe necessary blood concentration of heparin in a patient undergoingsurgery of a type requiring blood to be removed from the patient andthen returned to the patient, as when using a heart-lung machine duringcardiac surgery. It is contemplated that this will reduce thecomplications of surgery involving the passage of blood through such avessel, by reducing the bleeding complications resulting from the use ofheparin.

VII.C.2. Another embodiment is a vessel including a wall and having aninner surface defining a lumen. The inner surface has an at leastpartial coating of a hydrophobic layer, the thickness of the coatingbeing from monomolecular thickness to about 1000 nm thick on the innersurface, the coating being effective to reduce the clotting or plateletactivation of blood exposed to the inner surface.

VII.C.3. Vessel Containing Viable Blood, Having a Coating of Group IIIor IV Element

VII.C.3. Another embodiment is a blood containing vessel having a wallhaving an inner surface defining a lumen. The inner surface has an atleast partial coating of a composition comprising one or more elementsof Group III, one or more elements of Group IV, or a combination of twoor more of these. The thickness of the coating is between monomolecularthickness and about 1000 nm thick, inclusive, on the inner surface. Thevessel contains blood viable for return to the vascular system of apatient disposed within the lumen in contact with the hydrophobic layer.

VII.C.4. Coating of Group III or IV Element Reduces Clotting or PlateletActivation of Blood in the Vessel

VII.C.4. Optionally, in the vessel of the preceding paragraph, thecoating of the Group III or IV Element is effective to reduce theclotting or platelet activation of blood exposed to the inner surface ofthe vessel wall.

VII.D. Pharmaceutical Delivery Vessels

VII.D. A coated vessel or container as described herein can be used forpreventing or reducing the escape of a compound or composition containedin the vessel into the environment surrounding the vessel.

Further uses of the coating and vessel as described herein, which areapparent from any part of the description and claims, are alsocontemplated.

VII.D.1. Vessel Containing Insulin, Having a Coating Deposited from anOrganosilicon Precursor

VII.D.1. Another embodiment is an insulin containing vessel including awall having an inner surface defining a lumen. The inner surface has anat least partial coating of a hydrophobic layer, characterized asdefined in the Definition Section. The coating can be from monomolecularthickness to about 1000 nm thick on the inner surface. Insulin isdisposed within the lumen in contact with the Si_(w)O_(x)C_(y)H_(z)coating.

VII.D.1. Still another embodiment is an insulin containing vesselincluding a wall and having an inner surface defining a lumen. The innersurface has an at least partial coating of a hydrophobic layer,characterized as defined in the Definition Section, the thickness of thecoating being from monomolecular thickness to about 1000 nm thick on theinner surface. Insulin, for example pharmaceutical insulin FDA approvedfor human use, is disposed within the lumen in contact with thehydrophobic layer.

VII.D.1. It is contemplated that the incorporation of a hydrophobiclayer, characterized as defined in the Definition Section, will reducethe adhesion or precipitation forming tendency of the insulin in adelivery tube of an insulin pump, as compared to its properties incontact with an unmodified polymeric surface. This property iscontemplated to reduce or potentially eliminate the need for filteringthe insulin passing through the delivery tube to remove a solidprecipitate.

VII.D.2. Coating Deposited from an Organosilicon Precursor ReducesPrecipitation of Insulin in the Vessel

VII.D.2. Optionally, in the vessel of the preceding paragraph, thecoating of a hydrophobic layer is effective to reduce the formation of aprecipitate from insulin contacting the inner surface, compared to thesame surface absent the hydrophobic layer.

VII.D.2. Even another embodiment is a vessel again comprising a wall andhaving an inner surface defining a lumen. The inner surface includes anat least partial coating of a hydrophobic layer. The thickness of thecoating is in the range from monomolecular thickness to about 1000 nmthick on the inner surface. The coating is effective to reduce theformation of a precipitate from insulin contacting the inner surface.

VII.D.3. Vessel Containing Insulin, Having a Coating of Group III or IvElement

VII.D.3. Another embodiment is an insulin containing vessel including awall having an inner surface defining a lumen. The inner surface has anat least partial coating of a composition comprising carbon, one or moreelements of Group III, one or more elements of Group IV, or acombination of two or more of these. The coating can be frommonomolecular thickness to about 1000 nm thick on the inner surface.Insulin is disposed within the lumen in contact with the coating.

VII.D.4. Coating of Group III or IV Element Reduces Precipitation ofInsulin in the Vessel

VII.D.4. Optionally, in the vessel of the preceding paragraph, thecoating of a composition comprising carbon, one or more elements ofGroup III, one or more elements of Group IV, or a combination of two ormore of these, is effective to reduce the formation of a precipitatefrom insulin contacting the inner surface, compared to the same surfaceabsent the coating.

WORKING EXAMPLES Example 0 Basic Protocols for Forming and Coating Tubesand Syringe Barrels

The vessels tested in the subsequent working examples were formed andcoated according to the following exemplary protocols, except asotherwise indicated in individual examples. Particular parameter valuesgiven in the following basic protocols, e.g. the electric power andprocess gas flow, are typical values. Whenever parameter values werechanged in comparison to these typical values, this will be indicated inthe subsequent working examples. The same applies to the type andcomposition of the process gas.

Protocol for Forming COC Tube (Used, e.g., in Examples 1, 19)

Cyclic olefin copolymer (COC) tubes of the shape and size commonly usedas evacuated blood collection tubes (“COC tubes”) were injection moldedfrom Topas® 8007-04 cyclic olefin copolymer (COC) resin, available fromHoechst AG, Frankfurt am Main, Germany, having these dimensions: 75 mmlength, 13 mm outer diameter, and 0.85 mm wall thickness, each having avolume of about 7.25 cm³ and a closed, rounded end.

Protocol for Forming PET Tube (Used, e.g., in Examples 2, 4, 8, 9, 10)

Polyethylene terephthalate (PET) tubes of the type commonly used asevacuated blood collection tubes (“PET tubes”) were injection molded inthe same mold used for the Protocol for Forming COC Tube, having thesedimensions: 75 mm length, 13 mm outer diameter, and 0.85 mm wallthickness, each having a volume of about 7.25 cm³ and a closed, roundedend.

Protocol for Coating Tube Interior with SiO_(x) (used, e.g., in Examples1, 2, 4, 8, 9, 10, 18, 19)

The apparatus as shown in FIG. 2 with the sealing mechanism of FIG. 45,which is a specific contemplated embodiment, was used. The vessel holder50 was made from Delrin® acetal resin, available from E.I. du Pont deNemours and Co., Wilmington Del., USA, with an outside diameter of 1.75inches (44 mm) and a height of 1.75 inches (44 mm). The vessel holder 50was housed in a Delrin® structure that allowed the device to move in andout of the electrode (160).

The electrode 160 was made from copper with a Delrin® shield. TheDelrin® shield was conformal around the outside of the copper electrode160. The electrode 160 measured approximately 3 inches (76 mm) high(inside) and was approximately 0.75 inches (19 mm) wide.

The tube used as the vessel 80 was inserted into the vessel holder 50base sealing with Viton® O-rings 490, 504 (Viton® is a trademark ofDuPont Performance Elastomers LLC, Wilmington Del., USA) around theexterior of the tube (FIG. 45). The tube 80 was carefully moved into thesealing position over the extended (stationary) ⅛-inch (3-mm) diameterbrass probe or counter electrode 108 and pushed against a copper plasmascreen.

The copper plasma screen 610 was a perforated copper foil material (K&SEngineering, Chicago III., USA, Part #LXMUW5 copper mesh) cut to fit theoutside diameter of the tube, and was held in place by a radiallyextending abutment surface 494 that acted as a stop for the tubeinsertion (see FIG. 45). Two pieces of the copper mesh were fit snuglyaround the brass probe or counter electrode 108, insuring goodelectrical contact.

The brass probe or counter electrode 108 extended approximately 70 mminto the interior of the tube and had an array of #80 wire(diameter=0.0135 inch or 0.343 mm). The brass probe or counter electrode108 extended through a Swagelok® fitting (available from Swagelok Co.,Solon Ohio, USA) located at the bottom of the vessel holder 50,extending through the vessel holder 50 base structure. The brass probeor counter electrode 108 was grounded to the casing of the RF matchingnetwork.

The gas delivery port 110 was 12 holes in the probe or counter electrode108 along the length of the tube (three on each of four sides oriented90 degrees from each other) and two holes in the aluminum cap thatplugged the end of the gas delivery port 110. The gas delivery port 110was connected to a stainless steel assembly comprised of Swagelok®fittings incorporating a manual ball valve for venting, a thermocouplepressure gauge and a bypass valve connected to the vacuum pumping line.In addition, the gas system was connected to the gas delivery port 110allowing the process gases, oxygen and hexamethyldisiloxane (HMDSO) tobe flowed through the gas delivery port 110 (under process pressures)into the interior of the tube.

The gas system was comprised of a Aalborg® GFC17 mass flow meter (Part #EW-32661-34, Cole-Parmer Instrument Co., Barrington III. USA) forcontrollably flowing oxygen at 90 sccm (or at the specific flow reportedfor a particular example) into the process and a polyether ether ketone(“PEEK”) capillary (outside diameter, “OD” 1/16-inch (1.5-mm.), insidediameter, “ID” 0.004 inch (0.1 mm)) of length 49.5 inches (1.26 m). ThePEEK capillary end was inserted into liquid hexamethyldisiloxane(“HMDSO,” Alfa Aesar® Part Number L16970, NMR Grade, available fromJohnson Matthey PLC, London). The liquid HMDSO was pulled through thecapillary due to the lower pressure in the tube during processing. TheHMDSO was then vaporized into a vapor at the exit of the capillary as itentered the low pressure region.

To ensure no condensation of the liquid HMDSO past this point, the gasstream (including the oxygen) was diverted to the pumping line when itwas not flowing into the interior of the tube for processing via aSwagelok® 3-way valve. Once the tube was installed, the vacuum pumpvalve was opened to the vessel holder 50 and the interior of the tube.

An Alcatel rotary vane vacuum pump and blower comprised the vacuum pumpsystem. The pumping system allowed the interior of the tube to bereduced to pressure(s) of less than 200 mTorr while the process gaseswere flowing at the indicated rates.

Once the base vacuum level was achieved, the vessel holder 50 assemblywas moved into the electrode 160 assembly. The gas stream (oxygen andHMDSO vapor) was flowed into the brass gas delivery port 110 (byadjusting the 3-way valve from the pumping line to the gas delivery port110). Pressure inside the tube was approximately 300 mTorr as measuredby a capacitance manometer (MKS) installed on the pumping line near thevalve that controlled the vacuum. In addition to the tube pressure, thepressure inside the gas delivery port 110 and gas system was alsomeasured with the thermocouple vacuum gauge that was connected to thegas system. This pressure was typically less than 8 Torr.

Once the gas was flowing to the interior of the tube, the RF powersupply was turned on to its fixed power level. A ENI ACG-6 600 Watt RFpower supply was used (at 13.56 MHz) at a fixed power level ofapproximately 50 Watts. The output power was calibrated in this and allfollowing Protocols and Examples using a Bird Corporation Model 43 RFWatt meter connected to the RF output of the power supply duringoperation of the coating apparatus. The following relationship was foundbetween the dial setting on the power supply and the output power: RFPower Out=55.times.Dial Setting. In the priority applications to thepresent application, a factor 100 was used, which was incorrect. The RFpower supply was connected to a COMDEL CPMX1000 auto match which matchedthe complex impedance of the plasma (to be created in the tube) to the50 ohm output impedance of the ENI ACG-6 RF power supply. The forwardpower was 50 Watts (or the specific amount reported for a particularexample) and the reflected power was 0 Watts so that the applied powerwas delivered to the interior of the tube. The RF power supply wascontrolled by a laboratory timer and the power on time set to 5 seconds(or the specific time period reported for a particular example). Uponinitiation of the RF power, a uniform plasma was established inside theinterior of the tube. The plasma was maintained for the entire 5 secondsuntil the RF power was terminated by the timer. The plasma produced asilicon oxide coating of approximately 20 nm thickness (or the specificthickness reported in a particular example) on the interior of the tubesurface.

After coating, the gas flow was diverted back to the vacuum line and thevacuum valve was closed. The vent valve was then opened, returning theinterior of the tube to atmospheric pressure (approximately 760 Torr).The tube was then carefully removed from the vessel holder 50 assembly(after moving the vessel holder 50 assembly out of the electrode 160assembly).

Protocol for Coating Tube Interior with Hydrophobic Layer (Used, e.g.,in Example 9)

The apparatus as shown in FIG. 2 with the sealing mechanism of FIG. 45,which is a specific contemplated embodiment, was used. The vessel holder50 was made from Delrin® acetal resin, available from E.I. du Pont deNemours and Co., Wilmington Del., USA, with an outside diameter of 1.75inches (44 mm) and a height of 1.75 inches (44 mm). The vessel holder 50was housed in a Delrin structure that allowed the device to move in andout of the electrode (160).

The electrode 160 was made from copper with a Delrin® shield. TheDelrin® shield was conformal around the outside of the copper electrode160. The electrode 160 measured approximately 3 inches (76 mm) high(inside) and was approximately 0.75 inches (19 mm) wide.

The tube used as the vessel 80 was inserted into the vessel holder 50base sealing with Viton® O-rings 490, 504 (Viton® is a trademark ofDuPont Performance Elastomers LLC, Wilmington Del., USA) around theexterior of the tube (FIG. 45). The tube 80 was carefully moved into thesealing position over the extended (stationary) ⅛-inch (3-mm) diameterbrass probe or counter electrode 108 and pushed against a copper plasmascreen.

The copper plasma screen 610 was a perforated copper foil material (K&SEngineering, Chicago III., USA, Part #LXMUW5 copper mesh) cut to fit theoutside diameter of the tube, and was held in place by a radiallyextending abutment surface 494 that acted as a stop for the tubeinsertion (see FIG. 45). Two pieces of the copper mesh were fit snuglyaround the brass probe or counter electrode 108, insuring goodelectrical contact.

The brass probe or counter electrode 108 extended approximately 70 mminto the interior of the tube and had an array of #80 wire(diameter=0.0135 inch or 0.343 mm). The brass probe or counter electrode108 extended through a Swagelok® fitting (available from Swagelok Co.,Solon Ohio, USA) located at the bottom of the vessel holder 50,extending through the vessel holder 50 base structure. The brass probeor counter electrode 108 was grounded to the casing of the RF matchingnetwork.

The gas delivery port 110 was 12 holes in the probe or counter electrode108 along the length of the tube (three on each of four sides oriented90 degrees from each other) and two holes in the aluminum cap thatplugged the end of the gas delivery port 110. The gas delivery port 110was connected to a stainless steel assembly comprised of Swagelok®fittings incorporating a manual ball valve for venting, a thermocouplepressure gauge and a bypass valve connected to the vacuum pumping line.In addition, the gas system was connected to the gas delivery port 110allowing the process gases, oxygen and hexamethyldisiloxane (HMDSO) tobe flowed through the gas delivery port 110 (under process pressures)into the interior of the tube.

The gas system was comprised of a Aalborg® GFC17 mass flow meter (Part #EW-32661-34, Cole-Parmer Instrument Co., Barrington III. USA) forcontrollably flowing oxygen at 60 sccm (or at the specific flow reportedfor a particular example) into the process and a polyether ether ketone(“PEEK”) capillary (outside diameter, “OD” 1/16-inch (1.5-mm.), insidediameter, “ID” 0.004 inch (0.1 mm)) of length 49.5 inches (1.26 m). ThePEEK capillary end was inserted into liquid hexamethyldisiloxane(“HMDSO,” Alfa Aesar® Part Number L16970, NMR Grade, available fromJohnson Matthey PLC, London). The liquid HMDSO was pulled through thecapillary due to the lower pressure in the tube during processing. TheHMDSO was then vaporized into a vapor at the exit of the capillary as itentered the low pressure region.

To ensure no condensation of the liquid HMDSO past this point, the gasstream (including the oxygen) was diverted to the pumping line when itwas not flowing into the interior of the tube for processing via aSwagelok® 3-way valve. Once the tube was installed, the vacuum pumpvalve was opened to the vessel holder 50 and the interior of the tube.

An Alcatel rotary vane vacuum pump and blower comprised the vacuum pumpsystem. The pumping system allowed the interior of the tube to bereduced to pressure(s) of less than 200 mTorr while the process gaseswere flowing at the indicated rates.

Once the base vacuum level was achieved, the vessel holder 50 assemblywas moved into the electrode 160 assembly. The gas stream (oxygen andHMDSO vapor) was flowed into the brass gas delivery port 110 (byadjusting the 3-way valve from the pumping line to the gas delivery port110). Pressure inside the tube was approximately 270 mTorr as measuredby a capacitance manometer (MKS) installed on the pumping line near thevalve that controlled the vacuum. In addition to the tube pressure, thepressure inside the gas delivery port 110 and gas system was alsomeasured with the thermocouple vacuum gauge that was connected to thegas system. This pressure was typically less than 8 Torr.

Once the gas was flowing to the interior of the tube, the RF powersupply was turned on to its fixed power level. A ENI ACG-6 600 Watt RFpower supply was used (at 13.56 MHz) at a fixed power level ofapproximately 39 Watts. The RF power supply was connected to a COMDELCPMX1000 auto match which matched the complex impedance of the plasma(to be created in the tube) to the 50 ohm output impedance of the ENIACG-6 RF power supply. The forward power was 39 Watts (or the specificamount reported for a particular example) and the reflected power was 0Watts so that the applied power was delivered to the interior of thetube. The RF power supply was controlled by a laboratory timer and thepower on time set to 7 seconds (or the specific time period reported fora particular example). Upon initiation of the RF power, a uniform plasmawas established inside the interior of the tube. The plasma wasmaintained for the entire 7 seconds until the RF power was terminated bythe timer. The plasma produced a silicon oxide coating of approximately20 nm thickness (or the specific thickness reported in a particularexample) on the interior of the tube surface.

After coating, the gas flow was diverted back to the vacuum line and thevacuum valve was closed. The vent valve was then opened, returning theinterior of the tube to atmospheric pressure (approximately 760 Torr).The tube was then carefully removed from the vessel holder 50 assembly(after moving the vessel holder 50 assembly out of the electrode 160assembly).

Protocol for Forming COC Syringe Barrel (Used, e.g., in Examples 3, 5,11-18, 20)

Syringe barrels (“COC syringe barrels”), CV Holdings Part 11447, eachhaving a 2.8 mL overall volume (excluding the Luer fitting) and anominal 1 mL delivery volume or plunger displacement, Luer adapter type,were injection molded from Topas® 8007-04 cyclic olefin copolymer (COC)resin, available from Hoechst AG, Frankfurt am Main, Germany, havingthese dimensions: about 51 mm overall length, 8.6 mm inner syringebarrel diameter and 1.27 mm wall thickness at the cylindrical portion,with an integral 9.5 millimeter length needle capillary Luer adaptermolded on one end and two finger flanges molded near the other end.

Protocol for Coating COC Syringe Barrel Interior with SiO_(x) (Used,e.g. in Examples 3, 5, 18)

An injection molded COC syringe barrel was interior coated with SiO_(x).The apparatus as shown in FIG. 2 with the sealing mechanism of FIG. 45was modified to hold a COC syringe barrel with butt sealing at the baseof the COC syringe barrel. Additionally a cap was fabricated out of astainless steel Luer fitting and a polypropylene cap that sealed the endof the COC syringe barrel (illustrated in FIG. 26), allowing theinterior of the COC syringe barrel to be evacuated.

The vessel holder 50 was made from Delrin® with an outside diameter of1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The vesselholder 50 was housed in a Delrin® structure that allowed the device tomove in and out of the electrode 160.

The electrode 160 was made from copper with a Delrin® shield. TheDelrin® shield was conformal around the outside of the copper electrode160. The electrode 160 measured approximately 3 inches (76 mm) high(inside) and was approximately 0.75 inches (19 mm) wide. The COC syringebarrel was inserted into the vessel holder 50, base sealing with anViton® O-rings.

The COC syringe barrel was carefully moved into the sealing positionover the extended (stationary) ⅛-inch (3-mm.) diameter brass probe orcounter electrode 108 and pushed against a copper plasma screen. Thecopper plasma screen was a perforated copper foil material (K&SEngineering Part #LXMUW5 Copper mesh) cut to fit the outside diameter ofthe COC syringe barrel and was held in place by a abutment surface 494that acted as a stop for the COC syringe barrel insertion. Two pieces ofthe copper mesh were fit snugly around the brass probe or counterelectrode 108 insuring good electrical contact.

The probe or counter electrode 108 extended approximately 20 mm into theinterior of the COC syringe barrel and was open at its end. The brassprobe or counter electrode 108 extended through a Swagelok® fittinglocated at the bottom of the vessel holder 50, extending through thevessel holder 50 base structure. The brass probe or counter electrode108 was grounded to the casing of the RF matching network.

The gas delivery port 110 was connected to a stainless steel assemblycomprised of Swagelok® fittings incorporating a manual ball valve forventing, a thermocouple pressure gauge and a bypass valve connected tothe vacuum pumping line. In addition, the gas system was connected tothe gas delivery port 110 allowing the process gases, oxygen andhexamethyldisiloxane (HMDSO) to be flowed through the gas delivery port110 (under process pressures) into the interior of the COC syringebarrel.

The gas system was comprised of a Aalborg® GFC17 mass flow meter (ColeParmer Part # EW-32661-34) for controllably flowing oxygen at 90 sccm(or at the specific flow reported for a particular example) into theprocess and a PEEK capillary (OD 1/16-inch (3-mm) ID 0.004 inches (0.1mm)) of length 49.5 inches (1.26 m). The PEEK capillary end was insertedinto liquid hexamethyldisiloxane (Alfa Aesar® Part Number L16970, NMRGrade). The liquid HMDSO was pulled through the capillary due to thelower pressure in the COC syringe barrel during processing. The HMDSOwas then vaporized into a vapor at the exit of the capillary as itentered the low pressure region.

To ensure no condensation of the liquid HMDSO past this point, the gasstream (including the oxygen) was diverted to the pumping line when itwas not flowing into the interior of the COC syringe barrel forprocessing via a Swagelok® 3-way valve.

Once the COC syringe barrel was installed, the vacuum pump valve wasopened to the vessel holder 50 and the interior of the COC syringebarrel. An Alcatel rotary vane vacuum pump and blower comprised thevacuum pump system. The pumping system allowed the interior of the COCsyringe barrel to be reduced to pressure(s) of less than 150 mTorr whilethe process gases were flowing at the indicated rates. A lower pumpingpressure was achievable with the COC syringe barrel, as opposed to thetube, because the COC syringe barrel has a much smaller internal volume.

After the base vacuum level was achieved, the vessel holder 50 assemblywas moved into the electrode 160 assembly. The gas stream (oxygen andHMDSO vapor) was flowed into the brass gas delivery port 110 (byadjusting the 3-way valve from the pumping line to the gas delivery port110). The pressure inside the COC syringe barrel was approximately 200mTorr as measured by a capacitance manometer (MKS) installed on thepumping line near the valve that controlled the vacuum. In addition tothe COC syringe barrel pressure, the pressure inside the gas deliveryport 110 and gas system was also measured with the thermocouple vacuumgauge that was connected to the gas system. This pressure was typicallyless than 8 Torr.

When the gas was flowing to the interior of the COC syringe barrel, theRF power supply was turned on to its fixed power level. A ENI ACG-6 600Watt RF power supply was used (at 13.56 MHz) at a fixed power level ofapproximately 30 Watts. The RF power supply was connected to a COMDELCPMX1000 auto match that matched the complex impedance of the plasma (tobe created in the COC syringe barrel) to the 50 ohm output impedance ofthe ENI ACG-6 RF power supply. The forward power was 30 Watts (orwhatever value is reported in a working example) and the reflected powerwas 0 Watts so that the power was delivered to the interior of the COCsyringe barrel. The RF power supply was controlled by a laboratory timerand the power on time set to 5 seconds (or the specific time periodreported for a particular example).

Upon initiation of the RF power, a uniform plasma was established insidethe interior of the COC syringe barrel. The plasma was maintained forthe entire 5 seconds (or other coating time indicated in a specificexample) until the RF power was terminated by the timer. The plasmaproduced a silicon oxide coating of approximately 20 nm thickness (orthe thickness reported in a specific example) on the interior of the COCsyringe barrel surface.

After coating, the gas flow was diverted back to the vacuum line and thevacuum valve was closed. The vent valve was then opened, returning theinterior of the COC syringe barrel to atmospheric pressure(approximately 760 Torr). The COC syringe barrel was then carefullyremoved from the vessel holder 50 assembly (after moving the vesselholder 50 assembly out of the electrode 160 assembly).

Protocol for Coating COC Syringe Barrel Interior with OMCTS LubricityLayer (Used, e.g., in Examples 11, 12, 15-18, 20)

COC syringe barrels as previously identified were interior coated with alubricity layer. The apparatus as shown in FIG. 2 with the sealingmechanism of FIG. 45 was modified to hold a COC syringe barrel with buttsealing at the base of the COC syringe barrel. Additionally a cap wasfabricated out of a stainless steel Luer fitting and a polypropylene capthat sealed the end of the COC syringe barrel (illustrated in FIG. 26).The installation of a Buna-N O-ring onto the Luer fitting allowed avacuum tight seal, allowing the interior of the COC syringe barrel to beevacuated.

The vessel holder 50 was made from Delrin® with an outside diameter of1.75 inches (44 mm) and a height of 1.75 inches (44 mm). The vesselholder 50 was housed in a Delrin® structure that allowed the device tomove in and out of the electrode 160.

The electrode 160 was made from copper with a Delrin® shield. TheDelrin® shield was conformal around the outside of the copper electrode160. The electrode 160 measured approximately 3 inches (76 mm) high(inside) and was approximately 0.75 inches (19 mm) wide. The COC syringebarrel was inserted into the vessel holder 50, base sealing with Viton®O-rings around the bottom of the finger flanges and lip of the COCsyringe barrel.

The COC syringe barrel was carefully moved into the sealing positionover the extended (stationary) ⅛-inch (3-mm.) diameter brass probe orcounter electrode 108 and pushed against a copper plasma screen. Thecopper plasma screen was a perforated copper foil material (K&SEngineering Part #LXMUW5 Copper mesh) cut to fit the outside diameter ofthe COC syringe barrel and was held in place by a abutment surface 494that acted as a stop for the COC syringe barrel insertion. Two pieces ofthe copper mesh were fit snugly around the brass probe or counterelectrode 108 insuring good electrical contact.

The probe or counter electrode 108 extended approximately 20 mm (unlessotherwise indicated) into the interior of the COC syringe barrel and wasopen at its end. The brass probe or counter electrode 108 extendedthrough a Swagelok® fitting located at the bottom of the vessel holder50, extending through the vessel holder 50 base structure. The brassprobe or counter electrode 108 was grounded to the casing of the RFmatching network.

The gas delivery port 110 was connected to a stainless steel assemblycomprised of Swagelok® fittings incorporating a manual ball valve forventing, a thermocouple pressure gauge and a bypass valve connected tothe vacuum pumping line. In addition, the gas system was connected tothe gas delivery port 110 allowing the process gas,octamethylcyclotetrasiloxane (OMCTS) (or the specific process gasreported for a particular example) to be flowed through the gas deliveryport 110 (under process pressures) into the interior of the COC syringebarrel.

The gas system was comprised of a commercially available HoribaVC1310/SEF8240 OMCTS10SC 4CR heated mass flow vaporization system thatheated the OMCTS to about 100.degree. C. The Horiba system was connectedto liquid octamethylcyclotetrasiloxane (Alfa Aesar® Part Number A12540,98%) through a ⅛-inch (3-mm) outside diameter PFA tube with an insidediameter of 1/16 in (1.5 mm). The OMCTS flow rate was set to 1.25 sccm(or the specific organosilicon precursor flow reported for a particularexample). To ensure no condensation of the vaporized OMCTS flow pastthis point, the gas stream was diverted to the pumping line when it wasnot flowing into the interior of the COC syringe barrel for processingvia a Swagelok® 3-way valve.

Once the COC syringe barrel was installed, the vacuum pump valve wasopened to the vessel holder 50 and the interior of the COC syringebarrel. An Alcatel rotary vane vacuum pump and blower comprised thevacuum pump system. The pumping system allowed the interior of the COCsyringe barrel to be reduced to pressure(s) of less than 100 mTorr whilethe process gases were flowing at the indicated rates. A lower pressurecould be obtained in this instance, compared to the tube and previousCOC syringe barrel examples, because the overall process gas flow rateis lower in this instance.

Once the base vacuum level was achieved, the vessel holder 50 assemblywas moved into the electrode 160 assembly. The gas stream (OMCTS vapor)was flowed into the brass gas delivery port 110 (by adjusting the 3-wayvalve from the pumping line to the gas delivery port 110). Pressureinside the COC syringe barrel was approximately 140 mTorr as measured bya capacitance manometer (MKS) installed on the pumping line near thevalve that controlled the vacuum. In addition to the COC syringe barrelpressure, the pressure inside the gas delivery port 110 and gas systemwas also measured with the thermocouple vacuum gauge that was connectedto the gas system. This pressure was typically less than 6 Torr.

Once the gas was flowing to the interior of the COC syringe barrel, theRF power supply was turned on to its fixed power level. A ENI ACG-6 600Watt RF power supply was used (at 13.56 MHz) at a fixed power level ofapproximately 7.5 Watts (or other power level indicated in a specificexample). The RF power supply was connected to a COMDEL CPMX1000 automatch which matched the complex impedance of the plasma (to be createdin the COC syringe barrel) to the 50 ohm output impedance of the ENIACG-6 RF power supply. The forward power was 7.5 Watts and the reflectedpower was 0 Watts so that 7.5 Watts of power (or a different power leveldelivered in a given example) was delivered to the interior of the COCsyringe barrel. The RF power supply was controlled by a laboratory timerand the power on time set to 10 seconds (or a different time stated in agiven example).

Upon initiation of the RF power, a uniform plasma was established insidethe interior of the COC syringe barrel. The plasma was maintained forthe entire coating time, until the RF power was terminated by the timer.The plasma produced a lubricity layer on the interior of the COC syringebarrel surface.

After coating, the gas flow was diverted back to the vacuum line and thevacuum valve was closed. The vent valve was then opened, returning theinterior of the COC syringe barrel to atmospheric pressure(approximately 760 Torr). The COC syringe barrel was then carefullyremoved from the vessel holder 50 assembly (after moving the vesselholder 50 assembly out of the electrode 160 assembly).

Protocol for Coating COC Syringe Barrel Interior with HMDSO Coating(Used, e.g., in Examples 12, 15, 16, 17)

The Protocol for Coating COC Syringe Barrel Interior with OMCTSLubricity layer was also used for applying an HMDSO coating, exceptsubstituting HMDSO for OMCTS.

Example 1

V. In the following test, hexamethyldisiloxane (HMDSO) was used as theorganosilicon (“O—Si”) feed to PECVD apparatus of FIG. 2 to apply anSiO_(x) coating on the internal surface of a cyclic olefin copolymer(COC) tube as described in the Protocol for Forming COC Tube. Thedeposition conditions are summarized in the Protocol for Coating TubeInterior with SiO_(x) and Table 1. The control was the same type of tubeto which no barrier layer was applied. The coated and uncoated tubeswere then tested for their oxygen transmission rate (OTR) and theirwater vapor transmission rate (WVTR).

V. Referring to Table 1, the uncoated COC tube had an OTR of 0.215cc/tube/day. Tubes A and B subjected to PECVD for 14 seconds had anaverage OTR of 0.0235 cc/tube/day. These results show that the SiO_(x)coating provided an oxygen transmission BIF over the uncoated tube of9.1. In other words, the SiO_(x) barrier layer reduced the oxygentransmission through the tube to less than one ninth its value withoutthe coating.

V. Tube C subjected to PECVD for 7 seconds had an OTR of 0.026. Thisresult shows that the SiO_(x) coating provided an OTR BIF over theuncoated tube of 8.3. In other words, the SiO_(x) barrier layer appliedin 7 seconds reduced the oxygen transmission through the tube to lessthan one eighth of its value without the coating.

V. The relative WVTRs of the same barrier layers on COC tubes were alsomeasured. The uncoated COC tube had a WVTR of 0.27 mg/tube/day. Tubes Aand B subjected to PECVD for 14 seconds had an average WVTR of 0.10mg/tube/day or less. Tube C subjected to PECVD for 7 seconds had a WVTRof 0.10 mg/tube/day. This result shows that the SiO_(x) coating provideda water vapor transmission barrier improvement factor (WVTR BIF) overthe uncoated tube of about 2.7. This was a surprising result, since theuncoated COC tube already has a very low WVTR.

Example 2

V. A series of PET tubes, made according to the Protocol for Forming PETTube, were coated with SiO_(x) according to the Protocol for CoatingTube Interior with SiO_(x) under the conditions reported in Table 2.Controls were made according to the Protocol for Forming PET Tube, butleft uncoated. OTR and WVTR samples of the tubes were prepared byepoxy-sealing the open end of each tube to an aluminum adaptor.

V. In a separate test, using the same type of coated PET tubes,mechanical scratches of various lengths were induced with a steel needlethrough the interior coating, and the OTR BIF was tested. Controls wereeither left uncoated or were the same type of coated tube without aninduced scratch. The OTR BIF, while diminished, was still improved overuncoated tubes (Table 2A).

V. Tubes were tested for OTR as follows. Each sample/adaptor assemblywas fitted onto a MOCON® Oxtran 2/21 Oxygen Permeability Instrument.Samples were allowed to equilibrate to transmission rate steady state(1-3 days) under the following test conditions:

-   -   Test Gas: Oxygen    -   Test Gas Concentration: 100%    -   Test Gas Humidity: 0% relative humidity    -   Test Gas Pressure: 760 mmHg    -   Test Temperature: 23.0.degree. C. (73.4.degree. F.)    -   Carrier Gas: 98% nitrogen, 2% hydrogen    -   Carrier Gas Humidity: 0% relative humidity

V. The OTR is reported as average of two determinations in Table 2.

V. Tubes were tested for WVTR as follows. The sample/adaptor assemblywas fitted onto a MOCON® Permatran-W 3/31 Water Vapor PermeabilityInstrument. Samples were allowed to equilibrate to transmission ratesteady state (1-3 days) under the following test conditions:

-   -   Test Gas: Water Vapor    -   Test Gas Concentration: NA    -   Test Gas Humidity: 100% relative humidity    -   Test Gas Temperature: 37.8 (.degree. C.) 100.0 (.degree. F.)    -   Carrier Gas: Dry nitrogen    -   Carrier Gas Humidity: 0% relative humidity

V. The WVTR is reported as average of two determinations in Table 2.

Example 3

A series of syringe barrels were made according to the Protocol forForming COC Syringe barrel. The syringe barrels were either barriercoated with SiO_(x) or not under the conditions reported in the Protocolfor Coating COC Syringe barrel Interior with SiO_(x) modified asindicated in Table 3.

OTR and WVTR samples of the syringe barrels were prepared byepoxy-sealing the open end of each syringe barrel to an aluminumadaptor. Additionally, the syringe barrel capillary ends were sealedwith epoxy. The syringe-adapter assemblies were tested for OTR or WVTRin the same manner as the PET tube samples, again using a MOCON® Oxtran2/21 Oxygen Permeability Instrument and a MOCON® Permatran-W 3/31 WaterVapor Permeability Instrument. The results are reported in Table 3.

Example 4 Composition Measurement of Plasma Coatings using X-RayPhotoelectron Spectroscopy (XPS)/Electron Spectroscopy for ChemicalAnalysis (ESCA) Surface Analysis

V.A. PET tubes made according to the Protocol for Forming PET Tube andcoated according to the Protocol for Coating Tube Interior with SiO_(x)were cut in half to expose the inner tube surface, which was thenanalyzed using X-ray photoelectron spectroscopy (XPS).

V.A. The XPS data was quantified using relative sensitivity factors anda model which assumes a homogeneous layer. The analysis volume is theproduct of the analysis area (spot size or aperture size) and the depthof information. Photoelectrons are generated within the X-raypenetration depth (typically many microns), but only the photoelectronswithin the top three photoelectron escape depths are detected. Escapedepths are on the order of 15-35 .ANG., which leads to an analysis depthof .about.50-100 .ANG. Typically, 95% of the signal originates fromwithin this depth.

V.A. Table 5 provides the atomic ratios of the elements detected. Theanalytical parameters used in for XPS are as follows:

Instrument PHI Quantum 2000 X-ray source Monochromated Alk_(α) 1486.6 eVAcceptance Angle ±23° Take-off angle 45° Analysis area 600 μm ChargeCorrection C1s 284.8 eV Ion Gun Conditions Ar⁺, 1 keV, 2 × 2 mm rasterSputter Rate 15.6 Å/min (SiO₂ Equivalent)

V.A. XPS does not detect hydrogen or helium. Values given are normalizedto Si=1 for the experimental number (last row) using the elementsdetected, and to O=1 for the uncoated polyethylene terephthalatecalculation and example. Detection limits are approximately 0.05 to 1.0atomic percent. Values given are alternatively normalized to 100% Si+O+Catoms.

V.A. The Inventive Example has an Si/O ratio of 2.4 indicating anSiO_(x) composition, with some residual carbon from incomplete oxidationof the coating. This analysis demonstrates the composition of an SiO_(x)barrier layer applied to a polyethylene terephthalate tube according tothe present invention.

V.A. Table 4 shows the thickness of the SiO_(x) samples, determinedusing TEM according to the following method. Samples were prepared forFocused Ion Beam (FIB) cross-sectioning by coating the samples with asputtered layer of platinum (50-100 nm thick) using a K575X Emitechcoating system. The coated samples were placed in an FEI FIB200 FIBsystem. An additional layer of platinum was FIB-deposited by injectionof an organo-metallic gas while rastering the 30 kV gallium ion beamover the area of interest. The area of interest for each sample waschosen to be a location half way down the length of the tube. Thin crosssections measuring approximately 15 .mu.m (“micrometers”) long, 2 .mu.mwide and 15 .mu.m deep were extracted from the die surface using aproprietary in-situ FIB lift-out technique. The cross sections wereattached to a 200 mesh copper TEM grid using FIB-deposited platinum. Oneor two windows in each section, measuring about 8 .mu.m wide, werethinned to electron transparency using the gallium ion beam of the FEIFIB.

V.C. Cross-sectional image analysis of the prepared samples wasperformed utilizing a Transmission Electron Microscope (TEM). Theimaging data was recorded digitally.

The sample grids were transferred to a Hitachi HF2000 transmissionelectron microscope. Transmitted electron images were acquired atappropriate magnifications. The relevant instrument settings used duringimage acquisition are given below.

Instrument Transmission Electron Microscope Manufacturer/Model HitachiHF2000 Accelerating Voltage 200 kV Condenser Lens 1 0.78 Condenser Lens2 0 Objective Lens 6.34 Condenser Lens Aperture #1 Objective LensAperture for #3 imaging Selective Area Aperture for SAD N/A

Example 5 Plasma Uniformity

V.A. COC syringe barrels made according to the Protocol for Forming COCSyringe barrel were treated using the Protocol for Coating COC SyringeBarrel Interior with SiO_(x), with the following variations. Threedifferent modes of plasma generation were tested for coating syringebarrels such as 250 with SiO_(x) films. V.A. In Mode 1, hollow cathodeplasma ignition was generated in the gas inlet 310, restricted area 292and processing vessel lumen 304, and ordinary or non-hollow-cathodeplasma was generated in the remainder of the vessel lumen 300.

V.A. In Mode 2, hollow cathode plasma ignition was generated in therestricted area 292 and processing vessel lumen 304, and ordinary ornon-hollow-cathode plasma was generated in the remainder of the vessellumen 300 and gas inlet 310.

V.A. In Mode 3, ordinary or non-hollow-cathode plasma was generated inthe entire vessel lumen 300 and gas inlet 310. This was accomplished byramping up power to quench any hollow cathode ignition. Table 6 showsthe conditions used to achieve these modes.

V.A. The syringe barrels 250 were then exposed to a ruthenium oxidestaining technique. The stain was made from sodium hypochlorite bleachand Ru^((III)) chloride hydrate. 0.2 g of Ru^((III)) chloride hydratewas put into a vial. 10 ml bleach were added and mixed thoroughly untilthe Ru^((III)) chloride hydrate dissolved.

V.A. Each syringe barrel was sealed with a plastic Luer seal and 3 dropsof the staining mixture were added to each syringe barrel. The syringebarrels were then sealed with aluminum tape and allowed to sit for 30-40minutes. In each set of syringe barrels tested, at least one uncoatedsyringe barrel was stained. The syringe barrels were stored with therestricted area 292 facing up.

V.A. Based on the staining, the following conclusions were drawn:

V.A.1. The stain started to attack the uncoated (or poorly coated) areaswithin 0.25 hours of exposure.

V.A.2. Ignition in the restricted area 292 resulted in SiO_(x) coatingof the restricted area 292.

V.A.3. The best syringe barrel was produced by the test with no hollowcathode plasma ignition in either the gas inlet 310 or the restrictedarea 292. Only the restricted opening 294 was stained, most likely dueto leaking of the stain.

V.A.4. Staining is a good qualitative tool to guide uniformity work.

V.A. Based on all of the above, we concluded:

V.A.1. Under the conditions of the test, hollow cathode plasma in eitherthe gas inlet 310 or the restricted area 292 led to poor uniformity ofthe coating.

V.A.2. The best uniformity was achieved with no hollow cathode plasma ineither the gas inlet 310 or the restricted area 292.

Example 6 Interference Patterns from Reflectance Measurements PropheticExample

VI.A. Using a UV-Visible Source (Ocean Optics DH2000-BAL DeuteriumTungsten 200-1000 nm), a fiber optic reflection probe (combinationemitter/collector Ocean Optics QR400-7 SR/BX with approximately 3 mmprobe area), miniature detector (Ocean Optics HR4000CG UV-NIRSpectrometer), and software converting the spectrometer signal to atransmittance/wavelength graph on a laptop computer, an uncoated PETtube Becton Dickinson (Franklin Lakes, N.J., USA) Product No. 36670313.times.75 mm (no additives) is scanned (with the probe emitting andcollecting light radially from the centerline of the tube, thus normalto the coated surface) both about the inner circumference of the tubeand longitudinally along the inner wall of the tube, with the probe,with no observable interference pattern observed. Then a BectonDickinson Product No. 366703 13.times.75 mm (no additives) SiO_(x)plasma-coated BD 366703 tube is coated with a 20 nanometer thick SiO_(x)coating as described in Protocol for Coating Tube Interior with SiO_(x).This tube is scanned in a similar manner as the uncoated tube. A clearinterference pattern is observed with the coated tube, in which certainwavelengths were reinforced and others canceled in a periodic pattern,indicating the presence of a coating on the PET tube.

Example 7 Enhanced Light Transmission from Integrating Sphere Detection

VI.A. The equipment used was a Xenon light source (Ocean OpticsHL-2000-HP-FHSA-20 W output Halogen Lamp Source (185-2000 nm)), anIntegrating Sphere detector (Ocean Optics ISP-80-8-I) machined to accepta PET tube into its interior, and HR2000+ES Enhanced Sensitivity UV.VISspectrometer, with light transmission source and light receiver fiberoptic sources (QP600-2-UV-VIS-600 um Premium Optical FIBER, UV/VIS, 2m), and signal conversion software (SPECTRASUITE—Cross-platformSpectroscopy Operating SOFTWARE). An uncoated PET tube made according tothe Protocol for Forming PET Tube was inserted onto a TEFZEL Tube Holder(Puck), and inserted into the integrating sphere. With the Spectrasuitesoftware in absorbance mode, the absorption (at 615 nm) was set to zero.An SiO_(x) coated tube made according to the Protocol for Forming PETTube and coated according to the Protocol for Coating Tube Interior withSiO_(x) (except as varied in Table 16) was then mounted on the puck,inserted into the integrating sphere and the absorbance recorded at 615nm wavelength. The data is recorded in Table 16.

VI.A. With the SiO_(x) coated tubes, an increase in absorption relativeto the uncoated article was observed; increased coating times resultedin increased absorption. The measurement took less than one second.

VI.A. These spectroscopic methods should not be considered limited bythe mode of collection (for example, reflectance vs. transmittance vs.absorbance), the frequency or type of radiation applied, or otherparameters.

Example 8 Outgassing Measurement on PET

VI.B. Present FIG. 30, adapted from FIG. 15 of U.S. Pat. No. 6,584,828,is a schematic view of a test set-up that was used in a working examplefor measuring outgassing through an SiO_(x) barrier layer 348 appliedaccording to the Protocol for Coating Tube Interior with SiO_(x) on theinterior of the wall 346 of a PET tube 358 made according to theProtocol for Forming PET Tube seated with a seal 360 on the upstream endof a Micro-Flow Technology measurement cell generally indicated at 362.

VI.B. A vacuum pump 364 was connected to the downstream end of acommercially available measurement cell 362 (an Intelligent Gas LeakSystem with Leak Test Instrument Model ME2, with second generation IMFSsensor, (10 .mu./min full range), Absolute Pressure Sensor range: 0-10Torr, Flow measurement uncertainty: +/−5% of reading, at calibratedrange, employing the Leak-Tek Program for automatic data acquisition(with PC) and signatures/plots of leak flow vs. time. This equipment issupplied by ATC Inc.), and was configured to draw gas from the interiorof the PET vessel 358 in the direction of the arrows through themeasurement cell 362 for determination of the mass flow rate outgassedvapor into the vessel 358 from its walls.

VI.B. The measurement cell 362 shown and described schematically herewas understood to work substantially as follows, though this informationmight deviate somewhat from the operation of the equipment actuallyused. The cell 362 has a conical passage 368 through which the outgassedflow is directed. The pressure is tapped at two longitudinally spacedlateral bores 370 and 372 along the passage 368 and fed respectively tothe chambers 374 and 376 formed in part by the diaphragms 378 and 380.The pressures accumulated in the respective chambers 374 and 376 deflectthe respective diaphragms 378 and 380. These deflections are measured ina suitable manner, as by measuring the change in capacitance betweenconductive surfaces of the diaphragms 378 and 380 and nearby conductivesurfaces such as 382 and 384. A bypass 386 can optionally be provided tospeed up the initial pump-down by bypassing the measurement cell 362until the desired vacuum level for carrying out the test is reached.

VI.B. The PET walls 350 of the vessels used in this test were on theorder of 1 mm thick, and the coating 348 was on the order of 20 nm(nanometers) thick. Thus, the wall 350 to coating 348 thickness ratiowas on the order of 50,000:1.

VI.B. To determine the flow rate through the measurement cell 362,including the vessel seal 360, 15 glass vessels substantially identicalin size and construction to the vessel 358 were successively seated onthe vessel seal 360, pumped down to an internal pressure of 1 Torr, thencapacitance data was collected with the measurement cell 362 andconverted to an “outgassing” flow rate. The test was carried out twotimes on each vessel. After the first run, the vacuum was released withnitrogen and the vessels were allowed recovery time to reach equilibriumbefore proceeding with the second run. Since a glass vessel is believedto have very little outgassing, and is essentially impermeable throughits wall, this measurement is understood to be at least predominantly anindication of the amount of leakage of the vessel and connections withinthe measurement cell 362, and reflects little if any true outgassing orpermeation. The results are in Table 7.

VI.B. The family of plots 390 in FIG. 31 shows the “outgas” flow rate,also in micrograms per minute, of individual tubes corresponding to thesecond run data in previously-mentioned Table 7. Since the flow ratesfor the plots do not increase substantially with time, and are muchlower than the other flow rates shown, the flow rate is attributed toleakage.

VI.B. Table 8 and the family of plots 392 in FIG. 31 show similar datafor uncoated tubes made according to the Protocol for Forming PET Tube.

VI.B. This data for uncoated tubes shows much larger flow rates: theincreases are attributed to outgas flow of gases captured on or withinthe inner region of the vessel wall. There is some spread among thevessels, which is indicative of the sensitivity of the test to smalldifferences among the vessels and/or how they are seated on the testapparatus.

VI.B. Table 9 and the families of plots 394 and 396 in FIG. 31 showsimilar data for an SiO_(x) barrier layer 348 applied according to theProtocol for Coating PET Tube Interior with SiO_(x) on the interior ofthe wall 346 of a PET tube made according to the Protocol for FormingPET Tube.

VI.B. The family of curves 394 for the SiO_(x) coated, injection-moldedPET tubes of this example shows that the SiO_(x) coating acts as abarrier to limit outgassing from the PET vessel walls, since the flowrate is consistently lower in this test than for the uncoated PET tubes.(The SiO_(x) coating itself is believed to outgas very little.) Theseparation between the curves 394 for the respective vessels indicatesthat this test is sensitive enough to distinguish slightly differingbarrier efficacy of the SiO_(x) coatings on different tubes. This spreadin the family 394 is attributed mainly to variations in gas tightnessamong the SiO_(x) coatings, as opposed to variations in outgassing amongthe PET vessel walls or variations in seating integrity (which have amuch tighter family 392 of curves). The two curves 396 for samples 2 and4 are outliers, as demonstrated below, and their disparity from otherdata is believed to show that the SiO_(x) coatings of these tubes aredefective. This shows that the present test can very clearly separateout samples that have been processed differently or damaged.

VI.B. Referring to Tables 8 and 9 previously mentioned and FIG. 32, thedata was analyzed statistically to find the mean and the values of thefirst and third standard deviations above and below the mean (average).These values are plotted in FIG. 32.

VI.B. This statistical analysis first shows that samples 2 and 4 ofTable 9 representing coated PET tubes are clear outliers, more than +3standard deviations away from the mean. These outliers are, however,shown to have some barrier efficacy, as their flow rates are stillclearly distinguished from (lower than) those of the uncoated PET tubes.

VI.B. This statistical analysis also shows the power of an outgassingmeasurement to very quickly and accurately analyze the barrier efficacyof nano-thickness barrier layers and to distinguish coated tubes fromuncoated tubes (which are believed to be indistinguishable using thehuman senses at the present coating thickness). Referring to FIG. 32,coated PET vessels showing a level of outgassing three standarddeviations above the mean, shown in the top group of bars, have lessoutgassing than uncoated PET vessels showing a level of outgassing threestandard deviations below the mean, shown in the bottom group of bars.This data shows no overlap of the data to a level of certainty exceeding6.sigma. (six-sigma).

VI.B. Based on the success of this test, it is contemplated that thepresence or absence of an SiO_(x) coating on these PET vessels can bedetected in a much shorter test than this working example, particularlyas statistics are generated for a larger number of samples. This isevident, for example from the smooth, clearly separated families ofplots even at a time T=12 seconds for samples of 15 vessels,representing a test duration of about one second following the origin atabout T=11 seconds.

VI.B. It is also contemplated, based on this data, that a barrierefficacy for SiO_(x) coated PET vessels approaching that of glass orequal to glass can be obtained by optimizing SiO_(x) coating.

Example 9 Wetting Tension

Plasma Coated PET Tube Examples

VII.A.1.a.ii. The wetting tension method is a modification of the methoddescribed in ASTM D 2578. Wetting tension is a specific measure for thehydrophobicity or hydrophilicity of a surface. This method uses standardwetting tension solutions (called dyne solutions) to determine thesolution that comes nearest to wetting a plastic film surface forexactly two seconds. This is the film's wetting tension.

VII.A.1.a.ii. The procedure utilized is varied from ASTM D 2578 in thatthe substrates are not flat plastic films, but are tubes made accordingto the Protocol for Forming PET Tube and (except for controls) coatedaccording to the Protocol for Coating Tube Interior with Hydrophobiclayer. A silicone coated glass syringe (Becton Dickinson Hypak® PRTCglass prefillable syringe with Luer-lok® tip) (1 mL) was also tested.The results of this test are listed in Table 10.

VII.A.1.a.ii. Surprisingly, plasma coating of uncoated PET tubes (40dynes/cm) can achieve either higher (more hydrophilic) or lower (morehydrophobic) energy surfaces using the same hexamethyldisiloxane (HMDSO)feed gas, by varying the plasma process conditions. A thin(approximately 20-40 nanometers) SiO_(x) coating made according to theProtocol for Coating Tube Interior with SiO_(x) (data not shown in thetables) provides similar wettability as hydrophilic bulk glasssubstrates. A thin (less than about 100 nanometers) hydrophobic layermade according to the Protocol for Coating Tube Interior withHydrophobic layer provides similar non-wettability as hydrophobicsilicone fluids (data not shown in the tables).

Example 10 Vacuum Retention Study of Tubes Via Accelerated Ageing

VII.A.3 Accelerated ageing offers faster assessment of long termshelf-life products. Accelerated ageing of blood tubes for vacuumretention is described in U.S. Pat. No. 5,792,940, Column 1, Lines11-49.

VII.A.3 Three types of polyethylene terephthalate (PET) 13.times.75 mm(0.85 mm thick walls) molded tubes were tested:

-   -   Becton Dickinson Product No. 366703 13.times.75 mm (no        additives) tube (shelf life 545 days or 18 months), closed with        Hemogard® system red stopper and uncolored guard [commercial        control];    -   PET tubes made according to the Protocol for Forming PET Tube,        closed with the same type of Hemogard® system red stopper and        uncolored guard [internal control]; and    -   injection molded PET 13.times.75 mm tubes, made according to the        Protocol for Forming PET Tube, coated according to the Protocol        for Coating Tube Interior with SiO_(x) closed with the same type        of Hemogard® system red stopper and uncolored guard [inventive        sample].

VII.A.3 The BD commercial control was used as received. The internalcontrol and inventive samples were evacuated and capped with the stoppersystem to provide the desired partial pressure (vacuum) inside the tubeafter sealing. All samples were placed into a three gallon (3.8 L) 304SS wide mouth pressure vessel (Sterlitech No. 740340). The pressurevessel was pressurized to 48 psi (3.3 atm, 2482 mmHg). Water volume drawchange determinations were made by (a) removing 3-5 samples atincreasing time intervals, (b) permitting water to draw into theevacuated tubes through a 20 gauge blood collection adaptor from a oneliter plastic bottle reservoir, (c) and measuring the mass change beforeand after water draw.

VII.A.3 Results are indicated on Table 11.

VII.A.3 The Normalized Average Decay Rate is calculated by dividing thetime change in mass by the number of pressurization days and initialmass draw [mass change/(days*initial mass)]. The Accelerated Time to 10%Loss (months) is also calculated. Both data are listed in Table 12.

VII.A.3 This data indicates that both the commercial control anduncoated internal control have identical vacuum loss rates, andsurprisingly, incorporation of a SiO_(x) coating on the PET interiorwalls improves vacuum retention time by a factor of 2.1.

Example 11 Lubricity Layers

VII.B.1.a. The following materials were used in this test:

-   -   Commercial (BD Hypak® PRTC) glass prefillable syringes with        Luer-lok® tip) (ca 1 mL)    -   COC syringe barrels made according to the Protocol for Forming        COC Syringe barrel;    -   Commercial plastic syringe plungers with elastomeric tips taken        from Becton Dickinson Product No. 306507 (obtained as saline        prefilled syringes);    -   Normal saline solution (taken from the Becton-Dickinson Product        No. 306507 prefilled syringes);    -   Dillon Test Stand with an Advanced Force Gauge (Model AFG-50N)    -   Syringe holder and drain jig (fabricated to fit the Dillon Test        Stand)

VII.B.1.a. The following procedure was used in this test.

VII.B.1.a. The jig was installed on the Dillon Test Stand. The platformprobe movement was adjusted to 6 in/min (2.5 mm/sec) and upper and lowerstop locations were set. The stop locations were verified using an emptysyringe and barrel. The commercial saline-filled syringes were labeled,the plungers were removed, and the saline solution was drained via theopen ends of the syringe barrels for re-use. Extra plungers wereobtained in the same manner for use with the COC and glass barrels.

VII.B.1.a. Syringe plungers were inserted into the COC syringe barrelsso that the second horizontal molding point of each plunger was evenwith the syringe barrel lip (about 10 mm from the tip end). Usinganother syringe and needle assembly, the test syringes were filled viathe capillary end with 2-3 milliliters of saline solution, with thecapillary end uppermost. The sides of the syringe were tapped to removeany large air bubbles at the plunger/fluid interface and along thewalls, and any air bubbles were carefully pushed out of the syringewhile maintaining the plunger in its vertical orientation.

VII.B.1.a. Each filled syringe barrel/plunger assembly was installedinto the syringe jig. The test was initiated by pressing the down switchon the test stand to advance the moving metal hammer toward the plunger.When the moving metal hammer was within 5 mm of contacting the top ofthe plunger, the data button on the Dillon module was repeatedly tappedto record the force at the time of each data button depression, frombefore initial contact with the syringe plunger until the plunger wasstopped by contact with the front wall of the syringe barrel.

VII.B.1.a. All benchmark and coated syringe barrels were run with fivereplicates (using a new plunger and barrel for each replicate).

VII.B.1.a. COC syringe barrels made according to the Protocol forForming COC Syringe barrel were coated with an OMCTS lubricity layeraccording to the Protocol for Coating COC Syringe Barrel Interior withOMCTS Lubricity layer, assembled and filled with saline, and tested asdescribed above in this Example for lubricity layers. The polypropylenechamber used per the Protocol for Coating COC Syringe Barrel Interiorwith OMCTS Lubricity layer allowed the OMCTS vapor (and oxygen, ifadded—see Table 13) to flow through the syringe barrel and through thesyringe capillary into the polypropylene chamber (although a lubricitylayer is not needed in the capillary section of the syringe in thisinstance). Several different coating conditions were tested, as shown inpreviously mentioned Table 13. All of the depositions were completed onCOC syringe barrels from the same production batch.

The coated samples were then tested using the plunger sliding force testper the protocol of this Example, yielding the results in Table 13, inEnglish and metric force units. The data shows clearly that low powerand no oxygen provided the lowest plunger sliding force for COC andcoated COC syringes. Note that when oxygen was added at lower power (6W) (the lower power being a favorable condition) the plunger slidingforce increased from 1.09 lb, 0.49 Kg (at Power=11 W) to 2.27 lb., 1.03Kg. This indicates that the addition of oxygen may not be desirable toachieve the lowest possible plunger sliding force.

VII.B.1.a. Note also that the best plunger sliding force (Power=11 W,plunger sliding force=1.09 lb, 0.49 Kg) was very near the currentindustry standard of silicone coated glass (plunger sliding force=0.58lb, 0.26 Kg), while avoiding the problems of a glass syringe such asbreakability and a more expensive manufacturing process. With additionaloptimization, values equal to or better than the current glass withsilicone performance are expected to be achieved.

VII.B.1.a. The samples were created by coating COC syringe barrelsaccording to the Protocol for Coating COC Syringe Barrel Interior withOMCTS Lubricity layer. An alternative embodiment of the technologyherein, would apply the lubricity layer over another thin film coating,such as SiO_(x), for example applied according to the Protocol forCoating COC Syringe barrel Interior with SiO_(x).

Example 12 Improved Syringe Barrel Lubricity Layer

VII.B.1.a. The force required to expel a 0.9 percent saline payload froma syringe through a capillary opening using a plastic plunger wasdetermined for inner wall-coated syringes.

VII.B.1.a. Three types of COC syringe barrels made according to theProtocol for Forming COC Syringe barrel were tested: one type having nointernal coating [Uncoated Control], another type with ahexamethyldisiloxane (HMDSO)-based plasma coated internal wall coating[HMDSO Control] according to the Protocol for Coating COC Syringe BarrelInterior with HMDSO Coating, and a third type with anoctamethylcyclotetrasiloxane [OMCTS-Inventive Example]-based plasmacoated internal wall coating applied according to the Protocol forCoating COC Syringe Barrel Interior with OMCTS Lubricity layer. Freshplastic plungers with elastomeric tips taken from BD ProductBecton-Dickinson Product No. 306507 were used for all examples. Salinefrom Product No. 306507 was also used.

VII.B.1.a. The plasma coating method and apparatus for coating thesyringe barrel inner walls is described in other experimental sectionsof this application. The specific coating parameters for the HMDSO-basedand OMCTS-based coatings are listed in the Protocol for Coating COCSyringe Barrel Interior with HMDSO Coating, the Protocol for Coating COCSyringe barrel Interior with OMCTS Lubricity layer, and Table 14.

VII.B.1.a. The plunger is inserted into the syringe barrel to about 10millimeters, followed by vertical filling of the experimental syringethrough the open syringe capillary with a separate saline-filledsyringe/needle system. When the experimental syringe has been filledinto the capillary opening, the syringe is tapped to permit any airbubbles adhering to the inner walls to release and rise through thecapillary opening.

VII.B.1.a. The filled experimental syringe barrel/plunger assembly isplaced vertically into a home-made hollow metal jig, the syringeassembly being supported on the jig at the finger flanges. The jig has adrain tube at the base and is mounted on Dillon Test Stand with AdvancedForce Gauge (Model AFG-50N). The test stand has a metal hammer, movingvertically downward at a rate of six inches (152 millimeters) perminute. The metal hammer contacts the extended plunger expelling thesaline solution through the capillary. Once the plunger has contactedthe syringe barrel/capillary interface the experiment is stopped.

VII.B.1.a. During downward movement of the metal hammer/extendedplunger, resistance force imparted on the hammer as measured on theForce Gauge is recorded on an electronic spreadsheet. From thespreadsheet data, the maximum force for each experiment is identified.

VII.B.1.a. Table 14 lists for each Example the Maximum Force averagefrom replicate coated COC syringe barrels and the Normalized MaximumForce as determined by division of the coated syringe barrel MaximumForce average by the uncoated Maximum Force average.

VII.B.1.a. The data indicates all OMCTS-based inner wall plasma coatedCOC syringe barrels (Inventive Examples C, E, F, G, H) demonstrate muchlower plunger sliding force than uncoated COC syringe barrels (uncoatedControl Examples A & D) and surprisingly, also much lower plungersliding force than HMDSO-based inner wall plasma coated COC syringebarrels (HMDSO control Example B). More surprising, an OMCTS-basedcoating over a silicon oxide (SiO_(x)) gas barrier layer maintainsexcellent low plunger sliding force (Inventive Example F). The bestplunger sliding force was Example C (Power=8, plunger sliding force=1.1lb, 0.5 Kg). It was very near the current industry standard of siliconecoated glass (plunger sliding force=0.58 lb., 0.26 Kg.), while avoidingthe problems of a glass syringe such as breakability and a moreexpensive manufacturing process. With additional optimization, valuesequal to or better than the current glass with silicone performance areexpected to be achieved.

Example 13 Fabrication of COC Syringe Barrel with Exterior CoatingProphetic Example

VII.B.1.c. A COC syringe barrel formed according to the Protocol forForming COC Syringe barrel is sealed at both ends with disposableclosures. The capped COC syringe barrel is passed through a bath ofDaran® 8100 Saran Latex (Owensboro Specialty Plastics). This latexcontains five percent isopropyl alcohol to reduce the surface tension ofthe composition to 32 dynes/cm). The latex composition completely wetsthe exterior of the COC syringe barrel. After draining for 30 seconds,the coated COC syringe barrel is exposed to a heating schedulecomprising 275.degree. F. (135.degree. C.) for 25 seconds (latexcoalescence) and 122.degree. F. (50.degree. C.) for four hours (finishcure) in respective forced air ovens. The resulting PVdC film is 1/10mil (2.5 microns) thick. The COC syringe barrel and PVdC-COC laminateCOC syringe barrel are measured for OTR and WVTR using a MOCON brandOxtran 2/21 Oxygen Permeability Instrument and Permatran-W 3/31 WaterVapor Permeability Instrument, respectively.

VII.B.1.c. Predicted OTR and WVTR values are listed in Table 15, whichshows the expected Barrier Improvement Factor (BIF) for the laminatewould be 4.3 (OTR-BIF) and 3.0 (WVTR-BIF), respectively.

Example 14 Atomic Compositions of PECVD Applied OMCTS and HMDSO Coatings

VII.B.4. COC syringe barrel samples made according to the Protocol forForming COC Syringe barrel, coated with OMCTS (according to the Protocolfor Coating COC Syringe Barrel Interior with OMCTS Lubricity layer) orcoated with HMDSO according to the Protocol for Coating COC SyringeBarrel Interior with HMDSO Coating were provided. The atomiccompositions of the coatings derived from OMCTS or HMDSO werecharacterized using X-Ray Photoelectron Spectroscopy (XPS).

VII.B.4. XPS data is quantified using relative sensitivity factors and amodel that assumes a homogeneous layer. The analysis volume is theproduct of the analysis area (spot size or aperture size) and the depthof information. Photoelectrons are generated within the X-raypenetration depth (typically many microns), but only the photoelectronswithin the top three photoelectron escape depths are detected. Escapedepths are on the order of 15-35 .ANG., which leads to an analysis depthof −50-100 .ANG. Typically, 95% of the signal originates from withinthis depth.

VII.B.4. The following analytical parameters were used:

-   -   Instrument: PHI Quantum 2000    -   X-ray source:: Monochromated Alk_(—)1486.6 eV    -   Acceptance Angle: +23°    -   Take-off angle: 45°    -   Analysis area: 600 μm    -   Change Correction: C1s 284.8 eV    -   Ion Gun Conditions: Ar+, 1 keV, 2×2 mm raster    -   Sputter Rate: 15.6 Å/min (SiO₂ Equivalent)

VII.B.4. Table 17 provides the atomic concentrations of the elementsdetected. XPS does not detect hydrogen or helium. Values given arenormalized to 100 percent using the elements detected. Detection limitsare approximately 0.05 to 1.0 atomic percent.

VII.B.4. From the coating composition results and calculated startingmonomer precursor elemental percent in Table 17, while the carbon atompercent of the HMDSO-based coating is decreased relative to startingHMDSO monomer carbon atom percent (54.1% down to 44.4%), surprisinglythe OMCTS-based coating carbon atom percent is increased relative to theOMCTS monomer carbon atom percent (34.8% up to 48.4%), an increase of 39atomic %, calculated as follows:100%[(48.4/34.8)−1]=39at.%.

Also, while the silicon atom percent of the HMDSO-based coating isalmost unchanged relative to starting HMDSO monomer silicon atom percent(21.8% to 22.2%), surprisingly the OMCTS-based coating silicon atompercent is significantly decreased relative to the OMCTS monomer siliconatom percent (42.0% down to 23.6%), a decrease of 44 atomic %. With boththe carbon and silicon changes, the OMCTS monomer to coating behaviordoes not trend with that observed in common precursor monomers (e.g.HMDSO). See, e.g., Hans J. Griesser, Ronald C. Chatelier, Chris Martin,Zoran R. Vasic, Thomas R. Gengenbach, George Jessup J. Biomed. Mater.Res. (Appl. Biomater.) 53: 235-243, 2000.

Example 15 Volatile Components from Plasma Coatings (“Outgassing”)

VII.B.4. COC syringe barrel samples made according to the Protocol forForming COC Syringe barrel, coated with OMCTS (according to the Protocolfor Coating COC Syringe Barrel Interior with OMCTS Lubricity layer) orwith HMDSO (according to the Protocol for Coating COC Syringe BarrelInterior with HMDSO Coating) were provided. Outgassing gaschromatography/mass spectroscopy (GC/MS) analysis was used to measurethe volatile components released from the OMCTS or HMDSO coatings.

VII.B.4. The syringe barrel samples (four COC syringe barrels cut inhalf lengthwise) were placed in one of the 1½″ (37 mm) diameter chambersof a dynamic headspace sampling system (CDS 8400 auto-sampler). Prior tosample analysis, a system blank was analyzed. The sample was analyzed onan Agilent 7890A Gas Chromatograph/Agilent 5975 Mass Spectrometer, usingthe following parameters, producing the data set out in Table 18:

GC Column: 30 m.times.0.25 mm DB-5MS (J&W Scientific), 0.25 .mu.m filmthickness [0872] Flow rate: 1.0 ml/min, constant flow mode [0873]Detector: Mass Selective Detector (MSD) [0874] Injection Mode: Splitinjection (10:1 split ratio) [0875] Outgassing Conditions: 1½″ (37 mm)Chamber, purge for three hour at 85.degree. C., flow 60 ml/min [0876]Oven temperature: 40.degree. C. (5 min.) to 300.degree. C. @10.degree.C./min.; hold for 5 min. at 300.degree. C.

-   -   GC Column 30 m×0.25 mm DB-5MS (J&W Scientific), 0.25 μm film        thickness    -   Flow rate: 1.0 ml/min, constant flow mode    -   Detector: Mass Selective Detector (MSD)    -   Injection mode: Split injection (10:1 split ratio)    -   Outgassing Conditions: 1½″ (37 mm) Chamber, purge for three hour        at 85° C., Flow 60 ml/mn    -   Oven temperature 40° C. (5 min.) to 300° C. at 10° C./min.; hold        for 5 min. at 300° C.

The outgassing results from Table 18 clearly indicated a compositionaldifferentiation between the HMDSO-based and OMCTS-based lubricity layerstested. HMDSO-based compositions outgassed trimethylsilanol [(Me)₃SiOH]but outgassed no measured higher oligomers containing repeating-(Me)₂SiO— moieties, while OMCTS-based compositions outgassed nomeasured trimethylsilanol [(Me)₃SiOH] but outgassed higher oligomerscontaining repeating -(Me)₂SiO— moieties. It is contemplated that thistest can be useful for differentiating HMDSO-based coatings fromOMCTS-based coatings.

Without limiting the invention according to the scope or accuracy of thefollowing theory, it is contemplated that this result can be explainedby considering the cyclic structure of OMCTS, with only two methylgroups bonded to each silicon atom, versus the acyclic structure ofHMDSO, in which each silicon atom is bonded to three methyl groups.OMCTS is contemplated to react by ring opening to form a diradicalhaving repeating -(Me)₂SiO— moieties which are already oligomers, andcan condense to form higher oligomers. HMDSO, on the other hand, iscontemplated to react by cleaving at one O—Si bond, leaving one fragmentcontaining a single O—Si bond that recondenses as (Me)₃SiOH and theother fragment containing no O—Si bond that recondenses as [(Me)₃Si]₂.

The cyclic nature of OMCTS is believed to result in ring opening andcondensation of these ring-opened moieties with outgassing of higher MWoligomers (26 ng/test). In contrast, HMDSO-based coatings are believednot to provide any higher oligomers, based on the relativelylow-molecular-weight fragments from HMDSO.

Example 16 Density Determination of Plasma Coatings Using X-RayReflectivity (XRR)

VII.B.4. Sapphire witness samples (0.5.times.0.5.times.0.1 cm) wereglued to the inner walls of separate PET tubes, made according to theProtocol for Forming PET tubes. The sapphire witness-containing PETtubes were coated with OMCTS or HMDSO (both according to the Protocolfor Coating COC Syringe Barrel Interior with OMCTS Lubricity layer,deviating all with 2.times. power). The coated sapphire samples werethen removed and X-ray reflectivity (XRR) data were acquired on aPANalytical X'Pert diffractometer equipped with a parabolic multilayerincident beam monochromator and a parallel plate diffracted beamcollimator. A two layer Si_(w)O_(x)C_(y)H_(z) model was used todetermine coating density from the critical angle measurement results.This model is contemplated to offer the best approach to isolate thetrue Si_(w)O_(x)C_(y)H_(z) coating. The results are shown in Table 19.

VII.B.4. From Table 17 showing the results of Example 14, the loweroxygen (28%) and higher carbon (48.4%) composition of OMCTS versus HMDSOwould suggest OMCTS should have a lower density, due to both atomic massconsiderations and valency (oxygen=2; carbon=4). Surprisingly, the XRRdensity results indicate the opposite would be observed, that is, theOMCTS density is higher than HMDSO density.

VII.B.4. Without limiting the invention according to the scope oraccuracy of the following theory, it is contemplated that there is afundamental difference in reaction mechanism in the formation of therespective HMDSO-based and OMCTS-based coatings. HMDSO fragments canmore easily nucleate or react to form dense nanoparticles which thendeposit on the surface and react further on the surface, whereas OMCTSis much less likely to form dense gas phase nanoparticles. OMCTSreactive species are much more likely to condense on the surface in aform much more similar to the original OMCTS monomer, resulting in anoverall less dense coating.

Example 17 Thickness Uniformity of PECVD Applied Coatings

VII.B.4. Samples were provided of COC syringe barrels made according tothe Protocol for Forming COC Syringe barrel and respectively coated withSiO_(x) according to the Protocol for Coating COC Syringe BarrelInterior with SiO_(x) or an OMCTS-based lubricity layer according to theProtocol for Coating COC Syringe Barrel Interior with OMCTS Lubricitylayer. Samples were also provided of PET tubes made according to theProtocol for Forming PET Tube, respectively coated and uncoated withSiO.sub.x according to the Protocol for Coating Tube Interior withSiO_(x) and subjected to an accelerated aging test. Transmissionelectron microscopy (TEM) was used to measure the thickness of thePECVD-applied coatings on the samples. The previously stated TEMprocedure of Example 4 was used. The method and apparatus described bythe SiO_(x) and lubricity layer protocols used in this exampledemonstrated uniform coating as shown in Table 20.

Example 18 Outgassing Measurement on COC

VI.B. COC tubes were made according to the Protocol for Forming COCTube. Some of the tubes were provided with an interior barrier layer ofSiO_(x) according to the Protocol for Coating Tube Interior with SiO_(x)and other COC tubes were uncoated. Commercial glass blood collectionBecton Dickinson 13.times.75 mm tubes having similar dimensions werealso provided as above. The tubes were stored for about 15 minutes in aroom containing ambient air at 45% relative humidity and 70.degree. F.(21.degree. C.), and the following testing was done at the same ambientrelative humidity. The tubes were tested for outgassing following theATC microflow measurement procedure and equipment of Example 8 (anIntelligent Gas Leak System with Leak Test Instrument Model ME2, withsecond generation IMFS sensor, (10 .mu./min full range), AbsolutePressure Sensor range: 0-10 Torr, Flow measurement uncertainty: +/−5% ofreading, at calibrated range, employing the Leak-Tek Program forautomatic data acquisition (with PC) and signatures/plots of leak flowvs. time). In the present case each tube was subjected to a 22-secondbulk moisture degassing step at a pressure of 1 mm Hg, was pressurizedwith nitrogen gas for 2 seconds (to 760 millimeters Hg), then thenitrogen gas was pumped down and the microflow measurement step wascarried out for about one minute at 1 millimeter Hg pressure.

VI.B. The result is shown in FIG. 57, which is similar to FIG. 31generated in Example 8. In FIG. 57, the plots for the uncoated COC tubesare at 630, the plots for the Si_(Ox) coated COC tubes are at 632, andthe plots for the glass tubes used as a control are at 634. Again, theoutgassing measurement began at about 4 seconds, and a few seconds laterthe plots 630 for the uncoated COC tubes and the plots 632 for theSiO_(x) barrier coated tubes clearly diverged, again demonstrating rapiddifferentiation between barrier coated tubes and uncoated tubes. Aconsistent separation of uncoated COC (>2 micrograms at 60 seconds)versus SiO_(x)-coated COC (less than 1.6 micrograms at 60 seconds) wasrealized.

Example 19 Lubricity Layers

VII.B.1.a. COC syringe barrels made according to the Protocol forForming COC Syringe Barrel were coated with a lubricity layer accordingto the Protocol for Coating COC Syringe Barrel Interior with OMCTSLubricity layer. The results are provided in Table 21. The results showthat the trend of increasing the power level, in the absence of oxygen,from 8 to 14 Watts was to improve the lubricity of the coating. Furtherexperiments with power and flow rates can provide further enhancement oflubricity.

Example 20 Lubricity Layers Hypothetical Example

VII.B.4. Injection molded cyclic olefin copolymer (COC) plastic syringebarrels are made according to the Protocol for Forming COC SyringeBarrel. Some are uncoated (“control”) and others are PECVD lubricitycoated according to the Protocol for Coating COC Syringe Barrel Interiorwith OMCTS Lubricity layer (“lubricated syringe”). The lubricatedsyringes and controls are tested to measure the force to initiatemovement of the plunger in the barrel (breakout force) and the force tomaintain movement of the plunger in the barrel (plunger sliding force)using a Genesis Packaging Automated Syringe Force Tester, Model AST.

VII.B.4. The test is a modified version of the ISO 7886-1:1993 test. Thefollowing procedure is used for each test. A fresh plastic plunger withelastomeric tip taken from Becton Dickinson Product No. 306507 (obtainedas saline prefilled syringes) is removed from the syringe assembly. Theelastomeric tip is dried with clean dry compressed air. The elastomerictip and plastic plunger are then inserted into the COC plastic syringebarrel to be tested with the plunger positioned even with the bottom ofthe syringe barrel. The filled syringes are then conditioned asnecessary to achieve the state to be tested. For example, if the testobject is to find out the effect of lubricant coating on the breakoutforce of syringes after storing the syringes for three months, thesyringes are stored for three months to achieve the desired state.

VII.B.4. The syringe is installed into a Genesis Packaging AutomatedSyringe Force Tester. The tester is calibrated at the start of the testper the manufacturer's specification. The tester input variables areSpeed=100 mm/minute, Range=10,000. The start button is pushed on thetester. At completion of the test, the breakout force (to initiatemovement of the plunger in the barrel) and the plunger sliding force (tomaintain movement) are measured, and are found to be substantially lowerfor the lubricated syringes than for the control syringes.

I. FIG. 59 shows a vessel processing system 20 according to an exemplaryembodiment of the present invention. The vessel processing system 20comprises, inter alia, a first processing station 5501 and a secondprocessing station 5502. Examples for such processing stations are forexample depicted in FIG. 1, reference numerals 24, 26, 28, 30, 32 and34.

I. The first vessel processing system 5501 contains a vessel holder 38which holds a seated vessel 80. Although FIG. 59 depicts a blood tube80, the vessel can also be, for example, a syringe body, a vial, acuvette, a catheter or a pipette. The vessel can, for example, be madeof glass or plastic. In case of plastic vessels, the first processingstation can also comprise a mold for molding the plastic vessel.

I. After the first processing at the first processing station (whichprocessing can comprise molding of the vessel, a first inspection of thevessel for defects, coating of the interior surface of the vessel and asecond inspection of the vessel for defects, for example of the interiorcoating), the vessel holder 38 is transported together with the vessel80 to a second vessel processing station 5502. This transportation isperformed by a conveyor arrangement 70, 72, 74. For example, a gripperor several grippers can be provided for gripping the vessel holder 38and/or the vessel 80 in order to move the vessel/holder combination tothe next processing station 5502. Alternatively, only the vessel can bemoved without the holder. However, it can be advantageous to move theholder together with the vessel in which case the holder is adapted suchthat it can be transported by the conveyor arrangement.

I. FIG. 60 shows a vessel processing system 20 according to anotherexemplary embodiment of the present invention. Again, two vesselprocessing stations 5501, 5502 are provided. Furthermore, additionalvessel processing stations 5503, 5504 are provided which are arranged inseries and in which the vessel can be processed, i.e. inspected and/orcoated.

I. A vessel can be moved from a stock or holding area to the leftprocessing station 5504. Alternatively, the vessel can be molded in thefirst processing station 5504. In any case, a first vessel processingstep is performed in the processing station 5504, such as molding,inspection and/or coating, which can be followed by a second inspection.Then, the vessel is moved to the next processing station 5501 via theconveyor arrangement 70, 72, 74. Typically, the vessel is moved togetherwith the vessel holder. Additional processing is performed in the secondprocessing station 5501 after which the vessel and holder are moved tothe next processing station 5502 in which more processing is performed.The vessel is then moved (again together with the holder) to the fourthprocessing station 5503 for a fourth processing, after which it isconveyed to storage.

I. Before and after each coating step or molding step or any other stepwhich manipulates the vessel an inspection of the whole vessel, of partof the vessel and for example of an interior surface of the vessel canbe performed. The result of each inspection can be transferred to acentral processing unit 5505 via a data bus 5507. Each processingstation can be connected to the data bus 5507. The processor 5505, whichcan be adapted in form of a central control and regulation unit,processes the inspection data, analyzes the data and determines whetherthe last processing step was successful.

I. If it is determined that the last processing step was not successful,because for example the coating comprises gaps or because the surface ofthe coating is determined to be irregular or not smooth enough, thevessel does not enter the next processing station but is either removedfrom the production process (see conveyor sections 7001, 7002, 7003,7004) or conveyed back in order to be re-processed.

I. The processor 5505 is connected to a user interface 5506 forinputting control or regulation parameters.

I. FIG. 61 shows a vessel processing station 5501 according to anexemplary embodiment of the present invention. The station comprises aPECVD apparatus 5701 for coating an interior surface of the vessel.Furthermore, several detectors 5702-5707 are provided for vesselinspection. Such detectors can for example be electrodes for performingelectric measurements, optical detectors, like CCD cameras, gasdetectors or pressure detectors.

I. a vessel holder 38 according to an exemplary embodiment of thepresent invention, together with several detectors 5702, 5703, 5704 andan electrode with gas inlet port 108, 110.

I. The electrode and the detector 5702 can be adapted to be moved intothe interior space of the vessel 80 when the vessel is seated on theholder 38.

I. The optical inspection can be performed during a coating step, forexample with the help of optical detectors 5703, 5704 which are arrangedoutside the seated vessel 80 or even with the help of an opticaldetector 5705 arranged inside the interior space of the vessel 80.

I. The detectors can comprise color filters such that differentwavelengths can be detected during the coating process. The processingunit 5505 analyzes the optical data and determines whether the coatingwas successful or not to a predetermined level of certainty. If it isdetermined that the coating was most probably unsuccessful, therespective vessel is separated from the processing system orre-processed.

While the invention has been illustrated and described in detail in thedrawings and foregoing description, such illustration and descriptionare to be considered illustrative or exemplary and not restrictive; theinvention is not limited to the disclosed embodiments. Other variationsto the disclosed embodiments can be understood and effected by thoseskilled in the art and practicing the claimed invention, from a study ofthe drawings, the disclosure, and the appended claims. In the claims,the word “comprising” does not exclude other elements or steps, and theindefinite article “a” or “an” does not exclude a plurality. The merefact that certain measures are recited in mutually different dependentclaims does not indicate that a combination of these measures cannot beused to advantage. Any reference signs in the claims should not beconstrued as limiting the scope.

TABLE 1 COATED COC TUBE OTR AND WVTR MEASUREMENT OTR WVTR O—Si O₂ (cc/(mg/ Coating Power Flow Flow Time Tube. Tube. ID (Watts) O—Si (sccm)(sccm) (sec) Day) Day) No 0.215 0.27 Coating A 50 HMDSO 6 90 14 0.0230.07 B 50 HMDSO 6 90 14 0.024 0.10 C 50 HMDSO 6 90 7 0.026 0.10

TABLE 2 COATED PET TUBE OTR AND WVTR MEASUREMENT OTR WVTR O—Si O₂ (cc/(mg/ Coating Power Flow Flow Time Tube. Tube. BIF BIF ID (Watts) O—Si(sccm) (sccm) (sec) Day) Day) (OTR) (WVTR) Uncoated 0.0078 3.65 — —Control SiO_(x) 50 HMDSO 6 90 3 0.0035 1.95 2.2 1.9

TABLE 2A COATED PET TUBE OTR WITH MECHANICAL SCRATCH DEFECTS MechanicalO—Si O₂ Treat Scratch OTR Power Flow Flow Time Length (cc/tube. ExampleO—Si (Watts) (sccm) (sccm) (sec) (mm) day)* OTR BIF Uncoated 0.0052Control Inventive HMDSO 50 6 90 3 0 0.0014 3.7 Inventive HMDSO 50 6 90 31 0.0039 1.3 Inventive HMDSO 50 6 90 3 2 0.0041 1.3 Inventive HMDSO 50 690 3 10 0.0040 1.3 Inventive HMDSO 50 6 90 3 20 0.0037 1.4 *average oftwo tubes

TABLE 3 COATED COC SYRINGE BARREL OTR AND WVTR MEASUREMENT O—Si O₂ OTRWVTR Flow Flow Coating (cc/ (mg/ Syringe O—Si Power Rate Rate TimeBarrel. Barrel. BIF BIF Example Coating Composition (Watts) (sccm)(sccm) (sec) Day) Day) (OTR) (WVTR) A Uncoated 0.032 0.12 Control BSiO_(x) HMDSO 44 6 90 7 0.025 0.11 1.3 1.1 Inventive Example C SiO_(x)HMDSO 44 6 105 7 0.021 0.11 1.5 1.1 Inventive Example D SiO_(x) HMDSO 506 90 7 0.026 0.10 1.2 1.2 Inventive Example E SiO_(x) HMDSO 50 6 90 140.024 0.07 1.3 1.7 Inventive Example F SiO_(x) HMDSO 52 6 97.5 7 0.0220.12 1.5 1.0 Inventive Example G SiO_(x) HMDSO 61 6 105 7 0.022 0.11 1.41.1 Inventive Example H SiO_(x) HMDSO 61 6 120 7 0.024 0.10 1.3 1.2Inventive Example I SiO_(x) HMDZ 44 6 90 7 0.022 0.10 1.5 1.3 InventiveExample J SiO_(x) HMDZ 61 6 90 7 0.022 0.10 1.5 1.2 Inventive Example KSiO_(x) HMDZ 61 6 105 7 0.019 0.10 1.7 1.2 Inventive Example

TABLE 4 SIO_(x) COATING THICKNESS (NANOMETERS) DETECTED BY TEM OxygenHMDSO Flow Thickness Power Flow Rate Rate Sample O—Si (nm) (Watts)(sccm) (sccm) Inventive HMDSO 25-50 39 6 60 Example A Inventive HMDSO20-35 39 6 90 Example B

TABLE 5 ATOMIC RATIOS OF THE ELEMENTS DETECTED (in parentheses,Concentrations in percent, normalized to 100% of elements detected)Plasma Sample Coating Si O C PET Tube - — 0.08 (4.6%)   1 (31.5%) 2.7(63.9%) Comparative Example Polyethylene —   1 (28.6%) 2.5 (71.4%)Terephthalate - Calculated Coated PET SiO_(x)    1 (39.1%) 2.4 (51.7%)0.57 (9.2%)  Tube - Inventive Example

TABLE 6 EXTENT OF HOLLOW CATHODE PLASMA IGNITION Hollow Cathode PlasmaStaining Sample Power Time Ignition Result A 25 Watts 7 sec No Ignitionin gas inlet 310, good Ignition in restricted area 292 B 25 Watts 7 secIgnition in gas inlet 310 and poor restricted area 292 C  8 Watts 9 secNo Ignition in gas inlet 310, better Ignition in restricted area 292 D30 Watts 5 sec No Ignition in gas inlet 310 or best restricted area 292

TABLE 7 FLOW RATE USING GLASS TUBES Glass Run #1 Run #2 Average Tube(μg/min.) (μg/min.) (μg/min.) 1 1.391 1.453 1.422 2 1.437 1.243 1.34 31.468 1.151 1.3095 4 1.473 1.019 1.246 5 1.408 0.994 1.201 6 1.328 0.9811.1545 7 Broken Broken Broken 8 1.347 0.909 1.128 9 1.171 0.91 1.040510  1.321 0.946 1.1335 11  1.15 0.947 1.0485 12  1.36 1.012 1.186 13 1.379 0.932 1.1555 14  1.311 0.893 1.102 15  1.264 0.928 1.096 Average1.343 1.023 1.183 Max 1.473 1.453 1.422 Min 1.15 0.893 1.0405 Max − Min0.323 0.56 0.3815 Std. Dev. 0.097781 0.157895 0.1115087

TABLE 8 FLOW RATE USING PET TUBES Uncoated Run #1 (μg/ Run #2 (μg/Average PET min.) min.) (μg/min.) 1 10.36 10.72 10.54 2 11.28 11.1 11.193 11.43 11.22 11.325 4 11.41 11.13 11.27 5 11.45 11.17 11.31 6 11.3711.26 11.315 7 11.36 11.33 11.345 8 11.23 11.24 11.235 9 11.14 11.2311.185 10  11.1 11.14 11.12 11  11.16 11.25 11.205 12  11.21 11.31 11.2613  11.28 11.22 11.25 14  10.99 11.19 11.09 15  11.3 11.24 11.27 Average11.205 11.183 11.194 Max 11.45 11.33 11.345 Min 10.36 10.72 10.54 Max −Min 1.09 0.61 0.805 Std. Dev. 0.267578 0.142862 0.195121

TABLE 9 FLOW RATE FOR SiO_(x) COATED PET TUBES Coated Run #1 Run #2Average PET (μg/min.) (μg/min.) (μg/min.) 1 6.834 6.655 6.7445 2 9.6829.513 Outliers 3 7.155 7.282 7.2185 4 8.846 8.777 Outliers 5 6.985 6.9836.984 6 7.106 7.296 7.201 7 6.543 6.665 6.604 8 7.715 7.772 7.7435 96.848 6.863 6.8555 10  7.205 7.322 7.2635 11  7.61 7.608 7.609 12  7.677.527 7.5985 13  7.715 7.673 7.694 14  7.144 7.069 7.1065 15  7.33 7.247.285 Average 7.220 7.227 7.224 Max 7.715 7.772 7.7435 Min 6.543 6.6556.604 Max − Min 1.172 1.117 1.1395 Std. Dev. 0.374267 0.366072 0.365902

TABLE 10 WETTING TENSION MEASUREMENT OF COATED AND UNCOATED TUBESWetting Tension Example Tube Coating (dyne/cm) Reference uncoated glass72 Inventive Example PET tube coated with 60 SiO_(X) according toSiO_(X) Protocol Comparative Example uncoated PET 40 Inventive ExamplePET tube coated 34 according to Hydrophobic layer Protocol ComparativeExample Glass (+silicone fluid) 30 glass syringe, Part No.

TABLE 11 WATER MASS DRAW (GRAMS) Pressurization Time (days) Tube 0 27 4681 108 125 152 231 BD PET (commercial 3.0 1.9 1.0 control) Uncoated PET4.0 3.1 2.7 (internal control) SiO_(x)-Coated PET 4.0 3.6 3.3 (inventiveexample)

TABLE 12 CALCULATED NORMALIZED AVERAGE VACUUM DECAY RATE AND TIME TO 10%VACUUM LOSS Normalized Average Decay rate (delta Time to 10% Loss TubemL/initial mL · da) (months) - Accelerated BD PET 0.0038 0.9 (commercialcontrol) Uncoated PET 0.0038 0.9 (internal control) SiO_(x)-Coated PET0.0018 1.9 (inventive example)

TABLE 13 O—Si O₂ Avg. Power, Flow, Flow, time Force, Sample (Watts)(sccm) (sccm) (sec) (lb.) St. dev. SYRINGE BARRELS WITH LUBRICITY LAYER,ENGLISH UNITS Glass with No No No No 0.58 0.03 Silicone coating coatingcoating coating Uncoated COC No No No No 3.04 0.71 coating coatingcoating coating A 11 6 0 7 1.09 0.27 B 17 6 0 14 2.86 0.59 C 33 6 0 143.87 0.34 D 6 6 90 30 2.27 0.49 Uncoated COC — — — — 3.9 0.6 SiO_(x) onCOC 4.0 1.2 E 11 1.25 0 5 2.0 0.5 F 11 2.5 0 5 2.1 0.7 G 11 5 0 5 2.60.6 H 11 2.5 0 10 1.4 0.1 I 22 5 0 5 3.1 0.7 J 22 2.5 0 10 3.3 1.4 K 225 0 5 3.1 0.4 SYRINGE BARRELS WITH LUBRICITY LAYER, METRIC UNITS Glasssyringe No No No No 0.26 0.01 with sprayed coating coating coatingcoating silicone Uncoated No No No No 1.38 0.32 COC coating coatingcoating coating A 11 6 0 7 0.49 0.12 B 17 6 0 14 1.29 0.27 C 33 6 0 141.75 0.15 D 6 6 90 30 1.03 0.22 Uncoated COC — — — 1.77 0.27 SiO_(x) onCOC, 1.81 0.54 per protocol E 11 1.25 — 5 0.91 0.23 F 11 2.5 — 5 0.950.32 G 11 5 — 5 1.18 0.27 H 11 2.5 — 10 0.63 0.05 I 22 5 — 5 1.40 0.32 J22 2.5 — 10 1.49 0.63 K 22 5 — 5 1.40 0.18

TABLE 14 PLUNGER SLIDING FORCE MEASUREMENTS OF HMDSO- AND OMCTS-BASEDPLASMA COATINGS Coating Coating Si-0 Coating Maximum Normalized TimeFlow Rate Power Force Maximum Example Description Monomer (sec) (sccm)(Watts) (lb, kg.) Force A uncoated 3.3, 1.5 1.0 Control B HMDSO HMDSO 76 8 4.1, 1.9 1.2 Coating C OMCTS OMCTS 7 6 8 1.1, 0.5 0.3 Lubricitylayer D uncoated 3.9, 1.8 1.0 Control E OMCTS OMCTS 7 6 11 2.0, 0.9 0.5Lubricity layer F Two Layer 1 COC 14 6 50 Coating Syringe Barrel +SiO_(x) 2 OMCTS 7 6 8 2.5, 1.1 0.6 Lubricity layer G OMCTS OMCTS 5 1.2511 2, 0.9 0.5 Lubricity layer H OMCTS OMCTS 10 1.25 11 1.4, 0.6 0.4Lubricity layer

TABLE 15 OTR AND WVTR MEASUREMENTS (Prophetic) OTR (cc/ WVTR Samplebarrel · day) (gram/barrel · day) COC syringe-Comparative Example 4.3 X3.0 Y PVdC-COC laminate COC syringe- X Y Inventive Example

TABLE 16 OPTICAL ABSORPTION OF SiO_(x) COATED PET TUBES (NORMALIZED TOUNCOATED PET TUBE) Average Coating Absorption (@ Sample Time 615 nm)Replicates St. dev. Reference (uncoated) — 0.002-0.014 4 Inventive A   3 sec 0.021 8 0.001 Inventive B 2 × 3 sec 0.027 10 0.002 Inventive C3 × 3 sec 0.033 4 0.003

TABLE 17 ATOMIC CONCENTRATIONS (IN PERCENT, NORMALIZED TO 100% OFELEMENTS DETECTED) AND TEM THICKNESS Plasma Sample Coating Si O CHMDSO-based Si_(w)O_(x)C_(y) 0.76 (22.2%) 1 (33.4%) 3.7 (44.4%) CoatedCOC syringe barrel OMCTS-based Si_(w)O_(x)C_(y) 0.46 (23.6%) 1 (28%)  4.0 (48.4%) Coated COC syringe barrel HMDSO Monomer- Si₂OC₆   2 (21.8%)1 (24.1%)   6 (54.1%) calculated OMCTS Monomer- Si₄O₄C₈  1 (42%) 1(23.2%)   2 (34.8%) calculated

TABLE 18 VOLATILE COMPONENTS FROM SYRINGE OUTGASSING Coating Me₃SiOHHigher SiOMe Monomer (ng/test) oligomers (ng/test) Uncoated COCsyringe - Uncoated ND ND Comparative Example HMDSO-based Coated HMDSO 58ND COC syringe- Comparative Example OMCTS-based Coated OMCTS ND 26 COCsyringe-Inventive Example

TABLE 19 PLASMA COATING DENSITY FROM XRR DETERMINATION Density SampleLayer g/cm³ HMDSO-based Coated Sapphire - Si_(w)O_(x)C_(y)H_(z) 1.21Comparative Example OMCTS-based Coated Sapphire - Si_(w)O_(x)C_(y)H_(z)1.46 Inventive Example

TABLE 20 THICKNESS OF PECVD COATINGS BY TEM TEM TEM TEM Thickness SampleID Thickness I Thickness II III Protocol for Forming 164 nm  154 nm  167nm  COC Syringe Barrel; Protocol for Coating COC Syringe Barrel Interiorwith SiO_(x) Protocol for Forming 55 nm 48 nm 52 nm COC Syringe Barrel;Protocol for Coating COC Syringe Barrel Interior with OMCTS Lubricitylayer Protocol for 28 nm 26 nm 30 nm Forming PET Tube; Protocol forCoating Tube Interior with SiO_(x) Protocol for — — — Forming PET Tube(uncoated)

TABLE 21 OMCTS LUBRICITY LAYER PERFORMANCE (English Units) PercentAverage Force Plunger Reduction OMCTS Force (vs Power Flow Sample(lbs.)* uncoated) (Watts) (sccm) Comparative 3.99 — — — (no coating)Sample A 1.46 63% 14 0.75 Sample B 1.79 55% 11 1.25 Sample C 2.09 48% 81.75 Sample D 2.13 47% 14 1.75 Sample E 2.13 47% 11 1.25 Sample F 2.9925% 8 0.75 *Average of 4 replicates

TABLE 21 OMCTS LUBRICITY LAYER PERFORMANCE (Metric Units) PercentAverage Force Plunger Reduction OMCTS Force (vs Power Flow Sample(lbs.)* uncoated) (Watts) (sccm) Comparative 1.81 — — — (no coating)Sample A 0.66 63% 14 0.75 Sample B 0.81 55% 11 1.25 Sample C 0.95 48% 81.75 Sample D 0.96 47% 14 1.75 Sample E 0.96 47% 11 1.25 Sample F 1.3525% 8 0.75 Above force measurements are the average of 4 samples.

The invention claimed is:
 1. A method for inspecting the product of acoating process wherein a coating has been applied by plasma enhancedchemical vapor deposition (PECVD) to at least a portion of the surfaceof a vessel to form a coated surface, the method comprising: (a)providing a product of the coating process having a plasma enhancedchemical vapor deposition coating on the surface; (b) providing a spacethat is a lumen of the vessel adjacent to the plasma enhanced chemicalvapor deposition coating; (c) in a molecular flow mode of operation,measuring a release characteristic of at least one volatile species intothe space adjacent to the plasma enhanced chemical vapor depositioncoating; (d) identifying the release characteristic of the at least onevolatile species from an acceptably coated surface of the inspectionobject; and (e) determining whether the release characteristic measuredin step (c) satisfies the release characteristic identified in step (d).2. The method of claim 1, wherein the vessel is an evacuated bloodcollection tube, a syringe barrel, or a vial.
 3. The method of claim 1,further comprising connecting the lumen via a duct to a vacuum sourceand drawing at least a partial vacuum on the lumen before measuring therelease characteristic.
 4. The method of claim 3, further comprisingproviding an outgassing measurement cell communicating between the lumenand the vacuum source.
 5. The method of claim 3, in which the lumen isevacuated to a pressure from 0.1 Torr to 100 Torr.
 6. The method ofclaim 1, further comprising, before measuring the releasecharacteristic, contacting the coating with a gas.
 7. The method ofclaim 1, in which the gas comprises water vapor.
 8. The method of claim1, in which the gas comprises oxygen.
 9. The method of claim 1, in whichthe gas comprises carbon dioxide.
 10. The method of claim 1, in whichthe coating is a barrier layer having a thickness of less than 500 nm.11. The method of claim 10, in which the barrier layer comprisesSiO_(x), in which x, the atomic ratio of oxygen to silicon atoms, isfrom about 1.5 to about 2.9 as measured by X-ray photoelectronspectroscopy (XPS).
 12. The method of claim 10, in which the releasecharacteristic is measured under conditions effective to distinguish thepresence or absence of the barrier layer.
 13. The method of claim 12, inwhich the measurement of the presence or absence of the barrier layer isconfirmed to at least a six-sigma level of certainty.
 14. The method ofclaim 1, in which the plasma enhanced chemical vapor deposition coatingis prepared from an organosilicon precursor.
 15. The method of claim 1,in which the release characteristic is measured using micro-flowtechnology.
 16. The method of claim 1, in which the releasecharacteristic is measured by measuring the mass flow rate into thespace adjacent to the coated surface.
 17. The method of claim 16, inwhich the release characteristic is measured using micro-flowtechnology.
 18. A method for inspecting the product of a coating processwherein a coating has been applied by plasma enhanced chemical vapordeposition (PECVD) to at least a portion of the surface of a vessel toform a coated surface, the method comprising: (a) providing a product ofthe coating process having a plasma enhanced chemical vapor depositioncoating on the surface; (b) providing a space that is a lumen of thevessel adjacent to the plasma enhanced chemical vapor depositioncoating; (c) measuring a release characteristic of at least one volatilespecies into the space adjacent to the plasma enhanced chemical vapordeposition coating using micro-flow technology; (d) identifying therelease characteristic of the at least one volatile species from anacceptably coated surface of the inspection object; and (e) determiningwhether the release characteristic measured in step (c) satisfies therelease characteristic identified in step (d).
 19. The method of claim18, further comprising connecting the lumen via a duct to a vacuumsource and drawing at least a partial vacuum on the lumen beforemeasuring the release characteristic.
 20. The method of claim 19,further comprising providing an outgassing measurement cellcommunicating between the lumen and the vacuum source.
 21. The method ofclaim 19, in which the lumen is evacuated to a pressure from 0.1 Torr to100 Torr.
 22. The method of claim 18, further comprising, beforemeasuring the release characteristic, contacting the coating with a gas.23. The method of claim 18, in which the release characteristic ismeasured under conditions effective to distinguish the presence orabsence of the coating to at least a six-sigma level of certainty.
 24. Amethod for inspecting the product of a coating process wherein a coatinghas been applied by plasma enhanced chemical vapor deposition (PECVD) toat least a portion of the surface of a vessel to form a coated surface,the method comprising: (a) providing a product of the coating processhaving a plasma enhanced chemical vapor deposition coating on thesurface; (b) providing a space that is a lumen of the vessel adjacent tothe plasma enhanced chemical vapor deposition coating; (c) measuring arelease characteristic of at least one volatile species into the spaceadjacent to the plasma enhanced chemical vapor deposition coating bymeasuring the mass flow rate into the space adjacent to the coatedsurface; (d) identifying the release characteristic of the at least onevolatile species from an acceptably coated surface of the inspectionobject; and (e) determining whether the release characteristic measuredin step (c) satisfies the release characteristic identified in step (d).25. The method of claim 24, further comprising connecting the lumen viaa duct to a vacuum source and drawing at least a partial vacuum on thelumen before measuring the release characteristic.
 26. The method ofclaim 25, further comprising providing an outgassing measurement cellcommunicating between the lumen and the vacuum source.
 27. The method ofclaim 25, in which the lumen is evacuated to a pressure from 0.1 Torr to100 Torr.
 28. The method of claim 24, further comprising, beforemeasuring the release characteristic, contacting the coating with a gas.29. The method of claim 24, in which the release characteristic ismeasured under conditions effective to distinguish the presence orabsence of the coating to at least a six-sigma level of certainty. 30.The method of claim 24, in which the release characteristic is measuredusing micro-flow technology.